Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide

ABSTRACT

This disclosure provides for catalyst systems and processes for forming an α,β-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO 2 ); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/001,174, filed Jun. 6, 2018, which claims the benefit of priority ofU.S. Provisional Patent Application No. 62/519,556, filed Jun. 14, 2017,each of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

This disclosure relates to routes of synthesis of acrylic acid, otherα,β-unsaturated carboxylic acids and salts thereof, including catalyticmethods.

BACKGROUND

The majority of industrially synthesized chemical compounds are preparedfrom a limited set of precursors, whose ultimate sources are primarilyfossil fuels. As these reserves diminish, it would be beneficial to usea renewable resource, such as carbon dioxide, which is a non-toxic,abundant, and economical C₁ synthetic unit. The coupling of carbondioxide with other unsaturated molecules holds tremendous promise forthe direct preparation of molecules currently prepared by traditionalmethods not involving CO₂.

One could envision the direct preparation of acrylates and carboxylicacids through this method, when carbon dioxide is coupled with olefins.Currently, acrylic acid is produced by a two-stage oxidation ofpropylene. The production of acrylic acid directly from carbon dioxideand ethylene would represent a significant improvement due to thegreater availability of ethylene and carbon dioxide versus propylene,the use of a renewable material (CO₂) in the synthesis, and thereplacement of the two-step oxygenation process currently beingpracticed.

Therefore, what is needed are improved methods for preparing acrylicacid and other α,β-unsaturated carboxylic acids, including catalyticmethods.

SUMMARY OF THE DISCLOSURE

This summary is provided to introduce various concepts in a simplifiedform that are further described below in the detailed description. Thissummary is not intended to identify required or essential features ofthe claimed subject matter nor is the summary intended to limit thescope of the claimed subject matter.

In an aspect, this disclosure provides processes, including catalyticprocesses, for producing α,β-unsaturated carboxylic acids or saltsthereof utilizing a soluble or an insoluble form of a sulfonatedpolyaromatic resin system or a phosphonated polyaromatic resin system.When the sulfonated or the phosphonated polyaromatic resin system isinsoluble or the reaction system is otherwise heterogeneous, theseprocesses represent an improvement over homogeneous processes thatresult in poor yields and involve challenging separation and/orisolation procedures. Therefore, conventional methods generally makeisolation of the desired α,β-unsaturated carboxylic acid (e.g., acrylicacid) difficult. In contrast, the processes disclosed herein utilize asulfur oxoacid anion-substituted polyaromatic resin or a phosphorusoxoacid anion-substituted polyaromatic resin; wherein the polyaromaticresin further comprises associated metal cations that generally providesa heterogeneous reaction mixture. When combined with a catalyst such asa nickel catalyst, ethylene and carbon dioxide can be coupled to form ametalalactone, and the sulfonated or the phosphonated polyaromatic resincan subsequently destabilize the metalalactone which eliminates a metalacrylate. By developing the disclosed heterogeneous system, there is nowprovided a distinct advantage in ease of separation of the desiredproduct from the catalytic system. Moreover, the sulfonated or thephosphonated polyaromatic resin s can result in surprisingly high yieldsof the desired α,β-unsaturated carboxylic acid, such as acrylic acid.

According to an aspect, this disclosure provides a process for formingan α,β-unsaturated carboxylic acid or salt thereof, the processcomprising:

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.        According to this and other aspects of the disclosure, the        metalalactone compound may also be described as a metalalactone        comprising at least one ligand or simply a metalalactone, and        these terms are used interchangeably to reflect that the        metalalactone compound comprises at least one ligand in addition        to the metalalactone moiety. Similarly, reference to a        metalalactone ligand refers to any ligand of the metalalactone        compound other than the metalalactone moiety.

In another aspect, there is provided a process for forming anα,β-unsaturated carboxylic acid or a salt thereof, the processcomprising:

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations, to provide a reaction mixture comprising an            adduct of the metalalactone compound and sulfur oxoacid            anion-substituted polyaromatic resin or a phosphorus oxoacid            anion-substituted polyaromatic resin; and    -   b) applying reaction conditions to the reaction mixture suitable        to induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or the salt thereof.

Still another aspect of this disclosure provides a process for producingan α,β-unsaturated carboxylic acid or a salt thereof, the processcomprising:

-   -   a) contacting in any order        -   1) a transition metal precursor compound comprising at least            one first ligand;        -   2) optionally, at least one second ligand;        -   3) an olefin;        -   4) carbon dioxide (CO₂);        -   5) a diluent; and        -   6) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.

This summary and the following detailed description provide examples andare explanatory only of the invention. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Additional features or variations thereof can beprovided in addition to those set forth herein, such as for example,various feature combinations and sub-combinations of these described inthe detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE illustrates an embodiment or aspect of this disclosure,showing the use a sulfur oxoacid anion-substituted polyaromatic resin ora phosphorus oxoacid anion-substituted polyaromatic resin stationaryphase in a column configuration, in which formation of the acrylatecoupling reaction of ethylene and CO₂ to form a metalalactone such as anickelalactone in a mobile phase can be effected, and the resultingnickelalactone destabilized by the polyelectrolyte stationary phase toform an acrylate product.

DETAILED DESCRIPTION OF THE DISCLOSURE Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “asulfonated polyaromatic resin,” “a diluent,” “a catalyst,” and the like,is meant to encompass one, or mixtures or combinations of more than onesulfonated polyaromatic resin, diluent, catalyst, and the like, unlessotherwise specified.

The terms “including”, “with”, and “having”, as used herein, are definedas comprising (i.e., open language), unless specified otherwise.

The term “hydrocarbon” refers to a compound containing only carbon andhydrogen. Other identifiers can be utilized to indicate the presence ofparticular groups in the hydrocarbon, for instance, a halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon.

As used herein, the term “α,β-unsaturated carboxylic acid” and itsderivatives refer to a carboxylic acid having a carbon atom of acarbon-carbon double bond attached to the carbonyl carbon atom (thecarbon atom bearing the double bonded oxygen atom). Optionally, theα,β-unsaturated carboxylic acid can contain other functional groups,heteroatoms, or combinations thereof.

The term “polyelectrolyte” is used herein to mean a polymeric(macromolecular) substance which comprises a multiply-charged polyanion,polycation, or a copolymer thereof comprising of either a statistical orpredetermined distribution and/or sequencing of the individual monomerunits (e.g. block versus random copolymer). These polyions are generallystabilized by a stoichiometric amount of counter ions inherently presentin the polymeric substance. Therefore, an “anionic polyelectrolyte”refers to a polyelectrolyte that comprises a multiply-charged polyanion,together with an equivalent amount of cations. The charge on the polyiontypically resides on heteroatoms such as oxygen, nitrogen, or sulfur, oron groups such as sulfonate or phosphonate. The structural part of thepolyelectrolyte that bears the charged moieties can be pendant groupsoff a polymer backbone or can be part of the polymeric backbone itself.The term “polyelectrolyte” is used to refer to both soluble species andinsoluble species, such as some of the functionalizedpoly(vinylbenzene)-based materials and the phenol-formaldehyde typeresins described herein. For example, the sulfur oxoacidanion-substituted and the phosphorus oxoacid anion-substitutedpolystyrene type resins further comprise associated metal cations arereferred to as “polyelectrolytes”. The multiply-charged polyanion ofsuch polyelectrolytes may also be referred to as a base, and theassociated metal ions as simply a counter ion, metal ion, or Lewis acidas appropriate. As used herein, terms “polyelectrolyte” and “anionicpolyelectrolyte” are used interchangeably with terms such aspolyaromatic, polyaromatic polymer, polyaromatic resin, solid activator,and co-catalyst, and all these terms are used to refer to either theacid form of the polymer or its corresponding anionic polymer (saltform), as the context requires or allows.

The term “polyaromatic” or “polyaromatic resin” is used herein todescribe a neutral, acid form polymer or its corresponding anionic, saltform polymer derived therefrom, in which the aromatic moiety issubstituted with an acid-functional group that can be deprotonated toform an anionic polyelectrolyte comprising associated metal ions.Specifically, the polyaromatic resin of this disclosure is a sulfuroxoacid-substituted substituted polyaromatic resin or a phosphorusoxoacid-substituted polyaromatic resin, or salts thereof. Therefore, theterms “polyaromatic” or “polyaromatic resin” refer to the functionalizedforms. For example, the neutral, acid form polyaromatic resins of thisdisclosure include the sulfonic acid-substituted or the phosphonicacid-substituted polystyrene (poly(vinylbenzene)) polymers andcopolymers, or any suitable sulfonic acid-substituted or the phosphonicacid-substituted polymer. The anionic salt form polyaromatic resins ofthis disclosure include, for example, the sulfonated, the phosphonated,the sulfinated, the thiosulfonated and/or the thiosulfinated polystyrenepolymers and copolymers, or any suitable sulfonated, phosphonated,sulfinated, thiosulfonated, or thiosulfinated polymer. Moreover, termssuch as polyaromatic or polyaromatic resin are generally used herein todescribe specific types of polymers that are somewhat different fromeach other, as set out here.

[1] In one aspect, the term polyaromatic or polyaromatic resin are usedto describe a type of polymer that typically includes a pendant aromaticgroup bonded to a polymeric backbone, in which the pendant aromaticgroup is acid-functionalized or one in which the acid-functionalsubstituent on the pendant aromatic group has been converted to its saltform. Substituted analogs of these acid form and salt form polymers areencompassed in this group. For example, these terms describe the neutralsulfonic acid-substituted or the neutral phosphonic acid-substitutedpolystyrene polymers and copolymers (such as copolymers withdivinylbenzenes), and also used to describe the sulfonated or thephosphonated polystyrene polymers and copolymers, as the contextrequires or allows. Pyrolyzed variants of these polymers, which compriseporous carbonaceous materials are also included in this disclosure.

[2] According to another aspect, the term polyaromatic or polyaromaticresin are also generally used herein to describe, for example, anaromatic resin such as an extended crosslinked network derived fromphenolic (phenol-formaldehyde) resins, and comprising aromatic moietiesthat have been functionalized with sulfonic acid groups, phosphonic acidgroups, sulfinic acid groups, thiosulfonic acid groups and/orthiosulfinic acid groups. Generally, these resins are accessible fromeither reacting phenol compounds that are sulfur oxoacid acid oranion-functionalized and/or phosphorus acid or oxoacidanion-functionalized (e.g. sulfonated, phosphonated, sulfinated,thiosulfonated, and/or thiosulfinated) with formaldehyde underpolymerization conditions to form functionalized phenolic resins.Alternatively, these resins are also accessible by generating thephenolic (phenol-formaldehyde) resins in a conventional fashion andfunctionalizing these phenolic type resins with sulfonic acid groups,phosphonic acid groups, sulfinic acid groups, thiosulfonic acid groups,and/or thiosulfinic acid groups. Pyrolyzed variants of these phenolictype resins, which comprise porous carbonaceous materials are alsoincluded in this disclosure.

Examples of this type of polyaromatic resin include, but are not limitedto, sulfonated polyaromatic resins that can be generated by sulfuricacid treatment of a crosslinked polystyrene or a porous carbonaceousmaterial derived from the pyrolysis of a phenol formaldehyde resin.Other examples of this type of polyaromatic resin include, but are notlimited to, sulfur oxoacid anion-substituted polyaromatic resinsgenerated by SO₂ treatment (e.g. SO₂(aq)), sulfonic acid treatment,sulfinic acid treatment, thiosulfonic acid treatment, or thiosulfinicacid treatment of a crosslinked polystyrene or a porous carbonaceousmaterial derived from the pyrolysis of a phenol formaldehyde resin.Examples of this type of polyaromatic resin also include phosphonatedpolyaromatic resins that can be generated by phosphonic acid treatmentof a crosslinked polystyrene or a porous carbonaceous material derivedfrom the pyrolysis of a phenol formaldehyde resin. Phosphonatedpolyaromatic resins also may be generated by aromatic substitution witha chlorinated phosphine of a crosslinked polystyrene or a porouscarbonaceous material derived from the pyrolysis of a phenolformaldehyde resin, followed by for example, an alcoholic or aqueousworkup. The underlying phenol-formaldehyde crosslinked resins and theirsubstituted analogs that can be used in preparing the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin include the phenol aromatic groupand methylene moieties as part of an extended crosslinked network. Theskilled person will understand that pyrolysis of these materials cangenerate porous carbonaceous materials that can be functionalized asdescribed.

A “polyhydroxyarene” is used herein to a phenol-type monomer thatincludes more than one hydroxyl group. Resorcinol (also termed,benzenediol or m-dihydroxybenzene) is a typical polyhydroxyarene.Polyhydroxyarenes are used in the formation of Bakelite™ type resinswith formaldehyde, that can be further functionalized with a sulfuroxoacid or a phosphorus oxoacid, or a salt form thereof, such as asulfonate, phosphonate, sulfinated, thiosulfonated, or thiosulfinatedgroups.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all conformational isomers,regioisomers, stereoisomers, and mixtures thereof that can arise from aparticular set of substituents, unless otherwise specified. The name orstructure also encompasses all enantiomers, diastereomers, and otheroptical isomers (if there are any) whether in enantiomeric or racemicforms, as well as mixtures of stereoisomers, as would be recognized by askilled artisan, unless otherwise specified. For example, a generalreference to pentane includes n-pentane, 2-methyl-butane, and2,2-dimethylpropane; and a general reference to a butyl group includes an-butyl group, a sec-butyl group, an iso-butyl group, and a t-butylgroup.

Various numerical ranges are disclosed herein. When Applicants discloseor claim a range of any type, Applicants' intent is to disclose or claimindividually each possible number that such a range could reasonablyencompass, including end points of the range as well as any sub-rangesand combinations of sub-ranges encompassed therein, unless otherwisespecified. For example, by disclosing a temperature of from 70° C. to80° C., Applicant's intent is to recite individually 70° C., 71° C., 72°C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., and 80° C.,including any sub-ranges and combinations of sub-ranges encompassedtherein, and these methods of describing such ranges areinterchangeable. Moreover, all numerical end points of ranges disclosedherein are approximate, unless excluded by proviso. As a representativeexample, if Applicants disclose in an aspect of the disclosure that oneor more steps in the processes disclosed herein can be conducted at atemperature in a range from 10° C. to 75° C., this range should beinterpreted as encompassing temperatures in a range from “about” 10° C.to “about” 75° C.

Values or ranges may be expressed herein as “about”, from “about” oneparticular value, and/or to “about” another particular value. When suchvalues or ranges are expressed, other embodiments disclosed include thespecific value recited, from the one particular value, and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another embodiment. It will be furtherunderstood that there are a number of values disclosed therein, and thateach value is also herein disclosed as “about” that particular value inaddition to the value itself. In another aspect, use of the term “about”means±20% of the stated value, ±15% of the stated value, ±10% of thestated value, ±5% of the stated value, or ±3% of the stated value.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group of values or ranges, including any sub-rangesor combinations of sub-ranges within the group, that can be claimedaccording to a range or in any similar manner, if for any reasonApplicants choose to claim less than the full measure of the disclosure,for example, to account for a reference that Applicants can be unawareof at the time of the filing of the application. Further, Applicantsreserve the right to proviso out or exclude any individual substituents,analogs, compounds, ligands, structures, or groups thereof, or anymembers of a claimed group, if for any reason Applicants choose to claimless than the full measure of the disclosure, for example, to accountfor a reference that Applicants can be unaware of at the time of thefiling of the application.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe the compound or group wherein any non-hydrogen moiety formallyreplaces hydrogen in that group or compound, and is intended to benon-limiting. A compound or group can also be referred to herein as“unsubstituted” or by equivalent terms such as “non-substituted,” whichrefers to the original group or compound. “Substituted” is intended tobe non-limiting and include inorganic substituents or organicsubstituents as specified and as understood by one of ordinary skill inthe art.

The terms “contact product,” “contacting,” and the like, are used hereinto describe compositions and methods wherein the components arecontacted together in any order, in any manner, and for any length oftime, unless specified otherwise. For example, the components can becontacted by blending or mixing. Further, unless otherwise specified,the contacting of any component can occur in the presence or absence ofany other component of the compositions and methods described herein.Combining additional materials or components can be done by any suitablemethod. Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can, and often does, includereaction products, it is not required for the respective components toreact with one another. Similarly, “contacting” two or more componentscan result in a reaction product or a reaction mixture. Consequently,depending upon the circumstances, a “contact product” can be a mixture,a reaction mixture, or a reaction product.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

The Abstract of this application is not intended to be used to construethe scope of the claims or to limit the scope of the subject matter thatis disclosed herein, but rather to satisfy the requirements of 37 C.F.R.§ 1.72(b), to enable the United States Patent and Trademark Office andthe public generally to determine quickly from a cursory inspection thenature and gist of the technical disclosure. Moreover, any headings thatare employed herein are also not intended to be used to construe thescope of the claims or to limit the scope of the subject matter that isdisclosed herein. Any use of the past tense to describe any exampleotherwise indicated as constructive or prophetic is not intended toreflect that the constructive or prophetic example has actually beencarried out.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

The present disclosure is directed generally to methods for formingα,β-unsaturated carboxylic acids, or salts thereof. An illustrativeexample of a suitable α,β-unsaturated carboxylic acid is acrylic acid.

According to one aspect, this disclosure provides for the formation ofan α,β-unsaturated carboxylic acids and salts thereof frommetalalactones and polyaromatics such as those functionalizedpolyaromatic resins described here. One example of the α,β-unsaturatedcarboxylic acid salt formation from exemplary metalalactones and asulfur oxoacid anion-substituted polyaromatic resin or a phosphorusoxoacid anion-substituted polyaromatic resin is illustrated in Scheme 1,which provides for a nickel catalytic coupling reaction between anolefin and CO₂ and formation of an acrylate. As explained herein, Scheme1 is not limiting but is exemplary, and each reactant, catalyst,polymer, and product are provided for illustrative purposes.

In Scheme 1, a transition metal catalyst as disclosed herein isillustrated generally by a nickel(0) catalyst at compound 1, and theolefin disclosed herein, generally an α-olefin, is illustrated generallyby ethylene. In the presence of the catalyst 1, the olefin couples withCO₂ to form the metalalactone 2. Metalalactone 2 is destabilized by itsinteraction with a sulfur oxoacid anion-substituted polyaromatic resinor a phosphorus oxoacid anion-substituted polyaromatic resin 3, examplesof which is shown in Scheme 1. Illustrated are metallated (e.g. sodium)sulfonated (3a), phosphonated (3b), sulfinated (3c), thiosulfonated(3d), or thiosulfinated (3e) poly(4-vinylbenzene). While not intendingto be bound by theory, the sulfur oxoacid anion-substituted and thephosphorus oxoacid anion-substituted polyaromatic resins, where thepolyaromatic resin further comprises associated metal cations, arethought to interact with metalalactone 2 in some fashion, for example toform an adduct of some type, such as one illustrated as intermediate 4.Reaction with the combined sulfonated (3a), phosphonated (3b),sulfinated (3c), thiosulfonated (3d), or thiosulfinated (3e)poly(4-vinylbenzene) and metalalactone 2 (or intermediate of some type,represented generally as 4) proceeds to eliminate or release the metalacrylate 6, for example, from adduct 4, and regenerates catalystcompound 1 and byproduct neutral polymer 5, namely, the correspondingsulfur oxoacid-substituted or the phosphorus oxoacid-substitutedpolyaromatic resin, illustrated as 5a-5d, which are regenerated to thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin 3a-3d, upon its reactionwith the base 7. Reference to the “neutral” polymers 5 is intended toreflect that the anionic form of the polymer has been partially orlargely converted back to the acid form, regardless of whether thepolymer 5 is completely neutral in charge. The participation of thepolar solvent and/or base in the elimination or release of the metalacrylate 6, is not fully understood at this time and may include directparticipation in the mechanism or simply solvating an acrylate saltwhich is insoluble in the diluent.

As illustrated, the oxoacid-substituted resins such as the sulfonicacid-, phosphonic acid-, sulfinic acid-, thiosulfonic acid-, orthiosulfinic acid-substituted aromatic resins can be regenerated to theanionic (salt) form reactant, for example poly(sodium4-vinylbenzenesulfonate) 3a, poly(sodium (4-vinylbenzene)phosphonate)3b, poly(sodium 4-vinylbenzenesulfinate) 3c, poly(sodium4-vinylbenzenethiosulfonate) 3d, and poly(sodium4-vinylbenzenethiosulfinate) 3e, upon their respective reactions withthe base 7. In other words, elimination of the metal acrylate, forexample from intermediate 4, occurs to regenerate catalyst compound 1and byproduct acid form polymer, as shown in Scheme 1, which can beregenerated to the anionic salt form reactant upon reaction of theseacid form polymers with a base 7. In the presence of additional ethyleneand CO₂, catalyst 1 is converted to metalalactone 2.

Therefore, in an aspect, the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin of this disclosure can comprise a sulfonatedpolyaromatic resin, a phosphonated polyaromatic resin, a sulfinatedpolyaromatic resin, a thiosulfonated polyaromatic resin, or athiosulfinated polyaromatic resin. For example, the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin can comprise a sulfonated-, aphosphonated-, a sulfinated-, a thiosulfonated-, or athiosulfinated-styrene polymer or copolymer, such as for example, astyrene-divinylarene copolymer including a styrene-divinylbenzenecopolymer. Moreover, the sulfur oxoacid anion-substituted polyaromaticresin or the phosphorus oxoacid anion-substituted polyaromatic resin canbe macroreticular. In this aspect, the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin has an average particle size from about 0.1 mm toabout 1.0 mm, or an average particle size from about 0.50 mm to about0.80 mm. In an aspect, the average or median particle size is measuredby either dynamic light scattering tests or by a laser diffractiontechnique. Examples of suitable sulfur oxoacid anion-substitutedpolyaromatic resin include the commercial AMBERLITE® or AMBERLYST®resins.

One exemplary base illustrated in Scheme 1 is a hydroxide base, but acarbonate base, similar inorganic bases, and a wide range of other basescan be used, particularly metal-containing bases. Metal containing basescan include any basic inorganic metal compound or mixture of compoundsthat contain metal cations or cation sources, for example, alkali andalkaline earth metal compounds such as oxides, hydroxides, alkoxides,aryloxides, amides, alkyl amides, arylamides, and carbonates likecalcium hydroxide. In an aspect, the reaction of Scheme 1 can beconducted using certain bases as disclosed, but if desired, otherorganic bases such as some alkoxide, aryloxide, amide, alkyl amide,arylamide bases, or the like can be excluded. Typically, the inorganicbases such as alkali metal hydroxides have been found to work well.

Generally, the sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resin (“anionicpolyelectrolyte”) further comprise associated metal cations used in theprocesses disclosed herein can comprise (or consist essentially of, orconsist of) an insoluble anionic polyelectrolyte, a soluble anionicpolyelectrolyte, or a combination thereof. That is, the anionicpolyelectrolyte material can be soluble, insoluble, or only partially orslightly soluble in the diluent or reaction mixture. It is furthercontemplated that mixtures or combinations of two or more anionicpolyelectrolytes can be employed in certain aspects of the disclosure.Therefore, the “anionic polyelectrolyte” is a polymeric material whichcomprises a multiply-charged polyanion, together with an equivalentamount of counter cations, and is used generally to refer to bothsoluble materials and insoluble materials.

In an aspect, the sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resin; wherein thepolyaromatic resin further comprises associated metal cations can beused in the absence of an alkoxide or aryloxide base. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, and/orsubstituted analogs thereof. That is, additional bases with theirassociated counter ions are not required to effect the processesdisclosed herein.

According to an aspect, the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin; wherein the polyaromatic resin further comprisesassociated metal cations can be used in the absence of a solid support.That is the sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin; wherein thepolyaromatic resin further comprises associated metal cations can beused in its natural polymeric form without being bonded to or supportedon any insoluble support, such as an inorganic oxide or mixed oxidematerial.

In an aspect, the term anionic polyelectrolyte is used herein to referto and include such polyelectrolytes that include sulfur oxoacidanion-substituted material or the phosphorus oxoacid anion-substitutedmaterial; wherein the anion-substituted materials further compriseassociated metal cations. Examples of associated metal cations caninclude, but are not limited to, alkali metal cation, alkaline earthcation, or metal cations having varying Lewis acidities. Accordingly,the anionic polyelectrolytes generally include materials such as apoly(styrene sulfonate) (e.g. 3a of Scheme 1), a poly(styrenephosphonate) (e.g. 3b of Scheme 1), a poly(styrene sulfinate) (e.g. 3cof Scheme 1), a poly(styrene thiosulfonate) (e.g. 3d of Scheme 1), apoly(styrene thiosulfinate) (e.g. 3e of Scheme 1), including copolymersof these styrenes with other comonomers. Further, the anionicpolyelectrolytes of this disclosure also generally include sulfonated-,phosphonated-, sulfinated-, thiosulfonated-, or thiosulfinated-resinssuch as phenol-formaldehyde resins, a polyhydroxyarene-formaldehyderesin (such as a resorcinol-formaldehyde resin), a polyhydroxyarene- andfluorophenol-formaldehyde resin (such as a resorcinol- and2-fluorophenol-formaldehyde resin), and similar materials, along withassociated metal cations. Polymers that generally fall under thephenol-formaldehyde type of crosslinked resins may be referred to aspolyaromatic resins. Co-polymers of these specific types of anionicpolyelectrolytes are also included in this disclosure. Thepolyelectrolyte core structure can be substituted on the polymerbackbone or the pendant groups with sulfur or phosphorus oxoacids (acidform) or anions (salt form) oxoacid anions. Moreover, substitutedvariations of these polymers are included in the term anionicpolyelectrolyte. For example, any of the anionic polyelectrolytes can besubstituted with electron-withdrawing groups or electron-donating groupsor even combinations thereof.

Anionic polyelectrolytes such as those used herein include associatedcations, particularly associated metal cations, including Lewis acidicmetal cations and cations with low Lewis acidity. According to anaspect, the associated metal cations can be an alkali metal, an alkalineearth metal, or any combination thereof. Typical associated metalcations can be, can comprise, or can be selected from lithium, sodium,potassium, rubidium, cesium, magnesium, calcium, strontium, barium,zinc, aluminum or gallium and the like. Generally, sodium or potassiumassociated metal cations have been found to work well. Therefore,cations with a range of Lewis acidities in the particular solvent can beuseful according to this disclosure.

One aspect of the disclosed process provides for using a sulfur oxoacidanion-substituted polyaromatic resin or a phosphorus oxoacidanion-substituted polyaromatic resin. In an aspect, the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin can comprise, consist essentiallyof, or consist of: a sodium vinylbenzenesulfonate polymer or copolymer,such as a sodium 4-vinylbenzenesulfonate polymer or copolymer; a sodiumvinylphenylphosphonate polymer or copolymer, such as a sodium(4-vinylphenyl)phosphonate polymer or copolymer; a sodiumvinylbenzenesulfinate polymer or copolymer, such as a sodium4-vinylbenzenesulfinate polymer or copolymer; a sodiumvinylbenzenethiosulfonate polymer or copolymer, such as a sodium4-vinylbenzenethiosulfonate polymer or copolymer; and/or a sodiumvinylbenzenethiosulfinate polymer or copolymer, such as a sodium4-vinylbenzenethiosulfinate polymer or copolymer. According to anaspect, the comonomer in these copolymers can be a divinylbenzene, suchas a 1,3-divinylbenzene or a 1,4-divinylbenzene. Moreover, associatedmetal cations other than sodium can be employed in the salt forms of thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resins, such as, for example,lithium, sodium, potassium, rubidium, cesium, magnesium, calcium,strontium, barium, zinc, aluminum or gallium, and the like.

In a further aspect, useful anionic polyelectrolytes can includephenol-formaldehyde resins, which are cross-linked materials derivedfrom the condensation reaction of phenol with formaldehyde, that aretreated with a base or a metal cation source. Advantages of usingtreated phenol-formaldehyde resins include their insolubility, whichallows the use of a range of solvents with these materials, and theirrelatively high phenol concentration that can be functionalized using ametal base such as an alkali metal hydroxide. An early version of thethermosetting phenol formaldehyde resins formed from the condensationreaction of phenol with formaldehyde is Bakelite™, and variousphenol-formaldehyde resins used herein may be referred to generically as“Bakelite” resins. In the context of this disclosure, the use of termssuch as Bakelite or general terms such as phenol-formaldehyde resinscontemplates that these materials will be treated with ametal-containing base or a metal cation source such as sodium hydroxideprior to their use in the processes disclosed.

In an aspect, the sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resin can bemacroporous, that is, can have an average pore diameter greater thanabout 50 nm. For example, the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin can have an average pore diameter from about 50 nm toabout 250 nm. Surface area, pore diameter, and pore volume were measuredby Brunauer, Emmett and Teller (BET) technique with nitrogen gas used asthe probe.

In an aspect, the sulfonated polyaromatic resin can be generated bysulfuric acid treatment of a crosslinked polystyrene or a porouscarbonaceous material derived from the pyrolysis of a phenolformaldehyde resin. Similarly, in another aspect, other sulfur oxoacidanion-substituted polyaromatic resins such as the sulfinatedpolyaromatic resin can generated by SO₂ treatment (e.g. SO₂(aq),commonly termed sulfurous acid), sulfonic acid treatment, or sulfinicacid treatment of a crosslinked polystyrene or a porous carbonaceousmaterial derived from the pyrolysis of a phenol formaldehyde resin. Thethiosulfonated and thiosulfinated polyaromatic resin can generated by,for example, thiosulfonic acid treatment or thiosulfinic acid treatmentof a crosslinked polystyrene or a porous carbonaceous material derivedfrom the pyrolysis of a phenol formaldehyde resin. According to anotheraspect, the phosphonated polyaromatic resin can be formed by aromaticsubstitution with a chlorinated phosphine, followed by alcoholic oraqueous workup, of a crosslinked polystyrene or a porous carbonaceousmaterial derived from the pyrolysis of a phenol formaldehyde resin.

Other useful anionic polyelectrolytes include substitutedphenol-formaldehyde resins that are also generally crosslinked intoinsoluble resins. These resins can be formed from the condensationreaction of one or more of phenol, a polyhydroxyarene such as resorcinol(also, benzenediol or m-dihydroxybenzene), and/or their substitutedanalogs with formaldehyde. Therefore, these materials include resinsmade with more than one phenol as co-monomer. These polymeric materialsalso can be sulfonated, phosphonated, sulfinated, thiosulfonated, orthiosufinated with the corresponding or suitable acid treatment.Subsequent treatment with bases such as NaOH or KOH also provides aready method of functionalizing the polyaromatic polymers for thereactivity described herein. In one example, a resin can be preparedusing the monomer combination of resorcinol (m-dihydroxybenzene) andfluorophenol monomers with formaldehyde, and these polymeric materialsalso can be sulfonated, phosphonated, sulfinated, thiosulfonated, orthiosufinated with the corresponding or suitable acid treatment.

For example, sulfonation and phosphonation of aromatic materials can beperformed by a treatment of the resin with the appropriate acid undervarious temperatures, concentrations, and diluent conditions. Theseoxoacid installations can be accelerated and selectively placed whensulfonated/halogenated aromatic substrates catalytically coupled withsulfonate/phosphonate precursors. For example, alkyl phosphites can beinstalled and subsequently hydrolyzed when a cross coupling catalystsuch as nickel(II) chloride or bromide is employed. Sulfination of anaryl group can occur by reducing the appropriate sulfonyl chloride(prepared from thionyl chloride treatment of the sulfonate) with areagent such as zinc dust, and also can occur using Grignard reagents,dialkyl zinc compounds, hydrogen/palladium catalyst systems,sodium/mercury amalgam, and other electron sources. Various approachesare described in Chem. Rev., 1951, 48 (1), pp 69-124, which isincorporated herein by reference in its entirety. Thiosulfination andthiosulfonation can proceed from a variety of routes. For example, oneutilized protocol involves the oxidative cleavage of disulfide linkages(introduced through sulfur-induced crosslinking of a polyaromaticmicrostructure), which can be performed using oxidation treatments ofvarious strengths (depending on whether thiosulfinate or thiosulfonatefunctionality is desired) including mCPBA, hydrogen peroxide, orsulfuryl chloride. Thionyl chloride treatment of such linkages canproduce sulfinyl chloride moieties which can be further treated withsodium sulfide or acid to afford the desired material. Subsequent base(e.g. sodium hydroxide or sodium chloride) treatment can be used togenerate the metal-stabilized anionic polyelectrolyte. Variousapproaches to these materials can be found in, for example, Fischmann,A. J.; Spiccia, L. Dalton Trans. 2011, 40, 12310, which is incorporatedherein by reference in its entirety.

In those aspects and embodiments in which polymer support variations areused and/or in which the polyelectrolyte itself is a solid that isinsoluble in the diluent of the reaction, such solid statepolyelectrolyte embodiments can have any suitable surface area, porevolume, and particle size, as would be recognized by those of skill inthe art. For instance, the solid polyelectrolyte can have a pore volumein a range from 0.1 to 2.5 mL/g, or alternatively, from 0.5 to 2.5 mL/g.In a further aspect, the solid polyelectrolyte can have a pore volumefrom 1 to 2.5 mL/g. Alternatively, the pore volume can be from 0.1 to1.0 mL/g. Additionally, or alternatively, the solid polyelectrolyte canhave a surface area in a range from 10 to 750 m²/g; alternatively, from100 to 750 m²/g; or alternatively, from 100 to 500 m²/g or alternativelyfrom 30 to 200 m²/g. In a further aspect, the solid polyelectrolyte canhave a surface area of from 100 to 400 m²/g, from 200 to 450 m²/g, orfrom 150 to 350 m²/g. The average particle size of the solidpolyelectrolyte can vary greatly depending upon the process specifics,however, average particle sizes in the range of from 5 to 500 μm, from10 to 250 μm, or from 25 to 200 μm, are often employed. Alternatively, ⅛inch (3.2 mm) to ¼ inch (6.4 mm) pellets or used. Surface area, porediameter, and pore volume were measured by Brunauer, Emmett and Teller(BET) technique with nitrogen gas used as the probe.

The present disclosure also provides for various modifications of thepolymeric anionic stationary phase (anionic polyelectrolytes), forexample, in a column or other suitable solid state configuration.Further various modifications of the polymeric anionic stationary phase(anionic polyelectrolytes), for example, in a column or other suitablesolid state configuration are useful in the processes disclosed herein.For example, acid-base reactions that generate the anionicpolyelectrolyte from the acid form of the polymer can be effected usinga wide range of metal bases, including alkali and alkaline hydroxides,alkoxides, aryloxides, amides, alkyl or aryl amides, and the like, suchthat an assortment of electrophiles can be used in nickelalactonedestabilization as demonstrated herein for the poly(vinylbenzenesulfonicacid) and poly(vinylbenzenephosphonic acid).

Polymer modifications can also include using variants of the sulfuroxoacid anion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resins, for example, by preparing variouspoly(vinylbenzene) polymers substituted with an oxyacid of sulfur or anoxyacid of phosphorus. As an example, various styrenes substituted witha protected oxyacid of sulfur or a protected oxyacid of phosphorus andhaving a variety of organic and inorganic substituents, such as alkyls,halogens, and heteroatom substituents, can be polymerized, and subjectedto hydrolysis or acidolysis. Such adjustments can provide flexibilityfor tailoring the reaction according to the specific olefin to becoupled with CO₂, the reaction rate, the catalytic turnover, as well asadditional reaction parameters and combinations of reaction parameters.

In a further aspect, polymer modifications can also include usingco-polymers based on, for example, the co-polymerization of a protectedoxoacid-substituted styrene with other monomers (e.g., styrenes and/or(meth)acrylates) to produce libraries of polymeric electrophiles. Such alibrary can be utilized to test and match the specific anionicpolyelectrolyte with the specific olefin, to improve or optimizereaction rate, catalytic turnover, reaction selectivity, and the like.Further polymer support variations can also be used, for example,polymers can be supported onto beads or other surfaces. Alternatively,one class of polymer support variation that is possible for use withthis technology is the cast polymer that can function as an ion exchangemembrane. Alternatively, the anionic polyelectrolyte can be unsupportedand used in the absence of any support.

Referring again to Scheme 1, the reaction with the combined sulfonated(3a), phosphonated (3b), sulfinated (3c), thiosulfonated (3d), orthiosulfinated (3e) poly(4-vinylbenzene) and metalalactone 2 (orintermediate of some type, represented generally as 4) proceeds toeliminate or release the metal acrylate 6, for example, from adduct 4,and regenerates catalyst compound 1 and byproduct neutral polymer 5a-5e,the corresponding sulfur oxoacid-substituted or the phosphorusoxoacid-substituted polyaromatic resin. These acid-form resins 5a-5e canbe regenerated to the sulfur oxoacid anion-substituted polyaromaticresin or the phosphorus oxoacid anion-substituted polyaromatic resin3a-3e, upon reaction with the base, such as the metal-containing baseshown as 7 in Scheme 1. For example, the metal in a metal-containingbase can be, but is not limited to, a metal of Groups 1, 2, 12 or 13,such as lithium, sodium, potassium, rubidium, cesium, magnesium,calcium, strontium, barium, zinc, aluminum, or gallium.

The step of regenerating the anionic polyelectrolyte can be effected bycontacting the anionic polyelectrolyte with a regenerative base 7comprising a metal cation following the formation of the α,β-unsaturatedcarboxylic acid or a salt thereof. A wide range of bases 7 can be usedfor this regeneration step. For example, the regenerative base 7 can beor can comprise metal-containing bases which can include any reactiveinorganic basic metal compound or mixture of compounds that containmetal cations or cation sources, for example, alkali and alkaline earthmetal compounds such as oxides, hydroxides, alkoxides, aryloxides,amides, alkyl amides, arylamides, and carbonates. Suitable bases includeor comprise, for example, carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, Ca(OH)₂, NaOH, KOH), alkoxides (e.g.,Al(O^(i)Pr)₃, Na(O^(t)Bu), Mg(OEt)₂), aryloxides (e.g. Na(OC₆H₅), sodiumphenoxide), sulfates (e.g. Na₂SO₄, K₂O₄, CaSO₄, MgSO₄), and the like. Inan aspect, certain sulfur oxoacid-substituted polyaromatic resins or aphosphorus oxoacid-substituted polyaromatic resins with particularlyacidic groups can be regenerated to the corresponding sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin upon their reaction with only ametal-containing salt such as sodium chloride. As an example, suchresins can have electron-withdrawing substituents situated ortho or parato the sulfur oxoacid functional group or phosphorus oxoacid functionalgroup on a polyaromatic resin, such that the anionic form can readilyform and only a metal-containing salt (or “metal salt”) such as sodiumchloride is required to regenerate the corresponding oxoacidanion-substituted polyaromatic resin. Typically, this regeneration stepfurther comprises or is followed by the step of washing the oxoacidanion-substituted polyaromatic resin with a solvent or the diluent.

In one aspect, the step of regenerating the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin can be carried out by contacting aby-product resin that is generated from the process with an aqueoussodium ion (Nat) source, for example, aqueous sodium halide (brine). Inan aspect, the step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin can be effected by contacting a by-product resin thatis generated from the process with an aqueous acid and an aqueous brine,for example, by contacting the by-product resin with aqueous acidfollowed by aqueous brine, or by contacting the by-product resin withaqueous acid and aqueous brine at the same time. A wash step (e.g.aqueous) can be used, for example, when the by-product resin iscontacted with aqueous acid it can be washed with water prior tocontacting with aqueous brine. The aqueous brine solution is not limitedby concentration, for example, the aqueous solution can contain about 5wt % to about 15 wt % sodium chloride.

According to an aspect, the regenerative base can be or can comprise anucleophilic base, for example a metal hydroxide or metal alkoxide.While the regenerative base can comprise a non-nucleophilic base, theprocesses disclosed herein work in the absence of a non-nucleophilicbase such an alkali metal hydride or an alkaline earth metal hydride, analkali metal or alkaline earth metal dialkylamides and diarylamides, analkali metal or alkaline earth metal hexalkyldisilazane, and an alkalimetal or alkaline earth metal dialkylphosphides and diarylphosphides.

Typically, the inorganic bases such as alkali metal hydroxides or alkalimetal alkoxides have been found to work the best. However, in oneaspect, the reaction of Scheme 1 can be conducted using some bases butin the absence of certain other organic bases such as an alkoxide,aryloxide, amide, alkyl amide, arylamide, or the like. In anotheraspect, the anionic polyelectrolyte (and associated cations) can be usedand regenerated in the absence of an alkoxide or aryloxide. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, an amine, ahydride, a phosphazene, and/or substituted analogs thereof. For example,the processes disclosed herein can be conducted in the absence of sodiumhydride, an aryloxide salt (such as a sodium aryloxide), an alkoxidesalt (such as a sodium tert-butoxide), and/or a phosphazene.

The processes disclosed herein typically are conducted in the presenceof a diluent. Mixtures and combinations of diluents can be utilized inthese processes. The diluent can comprise, consist essentially of, orconsist of, any suitable solvent or any solvent disclosed herein, unlessotherwise specified. For example, the diluent can comprise, consistessentially of, or consist of a non-protic solvent, a protic solvent, anon-coordinating solvent, or a coordinating solvent. For instance, inaccordance with one aspect of this disclosure, the diluent can comprisea non-protic solvent. Representative and non-limiting examples ofnon-protic solvents can include tetrahydrofuran (THF), 2,5-Me₂THF,acetone, toluene, chlorobenzene, pyridine, carbon dioxide, olefin, andthe like, as well as combinations thereof. In accordance with anotheraspect, the diluent can comprise a weakly coordinating ornon-coordinating solvent. Representative and non-limiting examples ofweakly coordinating or non-coordinating solvents can include toluene,chlorobenzene, paraffins, halogenated paraffins, and the like, as wellas combinations thereof.

In accordance with yet another aspect, the diluent can comprise acarbonyl-containing solvent, for instance, ketones, esters, amides, andthe like, as well as combinations thereof. Representative andnon-limiting examples of carbonyl-containing solvents can includeacetone, ethyl methyl ketone, ethyl acetate, propyl acetate, butylacetate, isobutyl isobutyrate, methyl lactate, ethyl lactate,N,N-dimethylformamide, and the like, as well as combinations thereof. Instill another aspect, the diluent can comprise THF, 2,5-Me₂THF,methanol, acetone, toluene, chlorobenzene, pyridine, anisole, or acombination thereof; alternatively, THF; alternatively, 2,5-Me₂THF;alternatively, methanol; alternatively, acetone; alternatively, toluene;alternatively, chlorobenzene; or alternatively, pyridine.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an aromatic hydrocarbon solvent. Non-limiting examples ofsuitable aromatic hydrocarbon solvents that can be utilized singly or inany combination include benzene, toluene, xylene (inclusive ofortho-xylene, meta-xylene, para-xylene, or mixtures thereof), andethylbenzene, or combinations thereof; alternatively, benzene;alternatively, toluene; alternatively, xylene; or alternatively,ethylbenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) a halogenated aromatic hydrocarbon solvent. Non-limitingexamples of suitable halogenated aromatic hydrocarbon solvents that canbe utilized singly or in any combination include chlorobenzene,dichlorobenzene, and combinations thereof; alternatively, chlorobenzene;or alternatively, dichlorobenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an ether solvent. Non-limiting examples of suitable ethersolvents that can be utilized singly or in any combination includedimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether,di-n-butyl ether, diphenyl ether, methyl ethyl ether, methyl t-butylether, dihydrofuran, tetrahydrofuran (THF), 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, anisole, and combinations thereof;alternatively, diethyl ether, dibutyl ether, THF, 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, and combinations thereof;alternatively, THF; or alternatively, diethyl ether.

In a further aspect, any of these aforementioned diluents can beexcluded from the diluent or diluent mixture. For example, the diluentcan be absent a phenol or a substituted phenol, an alcohol or asubstituted alcohol, an amine or a substituted amine, water, an ether,an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, analdehyde or ketone, an ester or amide, and/or absent a halogenatedaromatic hydrocarbon, or any substituted analogs of these diluentshalogenated analogs, including any of the aforementioned diluents.Therefore, Applicant reserves the right to exclude any of the diluentsprovided herein.

In all aspects and embodiments disclosed herein, the diluent can includeor comprise carbon dioxide, olefin, or combinations thereof. At least aportion of the diluent can comprise the α,β-unsaturated carboxylic acidor the salt thereof, formed in the process.

In this disclosure, the term transition metal precursor, transitionmetal compound, transition metal catalyst, transition metal precursorcompound, carboxylation catalyst, transition metal precursor complex,transition metal-ligand, and similar terms refer to a chemical compoundthat serves as the precursor to the metalalactone, prior to the couplingof the olefin and carbon dioxide at the metal center of the transitionmetal precursor compound. Therefore, the metal of the transition metalprecursor compound and the metal of the metalalactone are the same. Insome aspects, some of the ligands of the transition metal precursorcompound carry over and are retained by the metalalactone following thecoupling reaction. In other aspects, the transition metal precursorcompound loses its existing ligands, referred to herein as firstligands, in presence of additional ligands such as chelating ligands,referred to herein as second ligands, as the metalalactone is formed.Therefore, the metalalactone generally incorporates the second (added)ligand(s), though in some aspects, the metalalactone can comprise thefirst ligand(s) that were bound in the transition metal precursorcompound.

According to an aspect, the transition metal catalyst or compound usedin the processes can be used without being immobilized on a solidsupport. That is the transition metal catalyst can be used is its usualform which is soluble in most useful solvents, without being bonded toor supported on any insoluble support, such as an inorganic oxide ormixed oxide material.

A prototypical example of a transition metal precursor compound thatloses its initial ligands in the coupling reaction in the presence of asecond (added) ligand, wherein the metalalactone incorporates the second(added) ligand(s), is contacting Ni(COD)₂ (COD is 1,5-cyclooctadiene)with a diphosphine ligand such as 1,2-bis(dicyclohexylphosphino)ethanein a diluent in the presence of ethylene and CO₂ to form anickelalactone with a coordinated 1,2-bis(dicyclohexylphosphino)ethanebidentate ligand.

In an aspect, any of the metalalactone ligand (that is, any ligand ofthe metalalactone compound other than the metalalactone moiety), thefirst ligand, or the second ligand can comprise at least one of anitrogen, phosphorus, sulfur, or oxygen heteroatom. For example, any ofthe metalalactone ligand, the first ligand, or the second ligandcomprises or is selected from a diphosphine ligand, a diamine ligand, adiene ligand, a diether ligand, or dithioether ligand. According toanother aspect, any of the metalalactone ligand, the first ligand, orthe second ligand comprises or is selected from a) an asymmetric ligand(comprising different donor atoms) such as 2-pyridylphosphine or b) anN-heterocyclic carbene (NHC) ligand.

Accordingly, in an aspect, the process for producing or forming anα,β-unsaturated carboxylic acid or a salt thereof, can comprise:

-   -   a) contacting in any order        -   1) a transition metal precursor compound comprising at least            one first ligand;        -   2) optionally, at least one second ligand;        -   3) an olefin;        -   4) carbon dioxide (CO₂);        -   5) a diluent; and        -   6) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.

Generally, the processes disclosed herein employ a metalalactone or atransition metal precursor compound or complex. The transition metal ofthe metalalactone, or of the transition metal precursor compound, can bea Group 3 to Group 8 transition metal or, alternatively, a Group 8 toGroup 11 transition metal. In one aspect, for instance, the metal of themetalalactone or the metal of the transition metal precursor compound isCr, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, W, Ag, Ir, Pt, or Au, while inanother aspect, the transition metal can be Fe, Ni, or Rh.Alternatively, the transition metal can be Cr; alternatively, thetransition metal can be Fe; alternatively, the transition metal can beCo; alternatively, the transition metal can be Ni; alternatively, thetransition metal can be Cu; alternatively, the transition metal can beMo; alternatively, the transition metal can be Ru; alternatively, thetransition metal can be Rh; alternatively, the transition metal can bePd; alternatively, the transition metal can be W; alternatively, thetransition metal can be Ag; alternatively, the transition metal can beIr; alternatively, the transition metal can be Pt; or alternatively, thetransition metal can Au.

In particular aspects contemplated herein, the transition metal can beNi. Hence, the metalalactone can be a nickelalactone and the transitionmetal precursor compound can be a Ni-ligand complex in these aspects.

The ligand of the metalalactone and/or of the transition metal precursorcompound, can be any suitable neutral electron donor group and/or Lewisbase. For instance, the suitable neutral ligands can include sigma-donorsolvents that contain a coordinating atom (or atoms) that can coordinateto the transition metal of the metalalactone (or of the transition metalprecursor compound). Examples of suitable coordinating atoms in theligands can include, but are not limited to, O, N, S, and P, orcombinations of these atoms. In some aspects, consistent with thisdisclosure, the ligand can be a bidentate ligand.

In an aspect, the ligand used to form the metalalactone and/or thetransition metal precursor compound can be an ether, an organiccarbonyl, a thioether, an amine, a nitrile, or a phosphine. In anotheraspect, the ligand used to form the metalalactone or the transitionmetal precursor compound can be an acyclic ether, a cyclic ether, anacyclic organic carbonyl, a cyclic organic carbonyl, an acyclicthioether, a cyclic thioether, a nitrile, an acyclic amine, a cyclicamine, an acyclic phosphine, or a cyclic phosphine.

Suitable ethers can include, but are not limited to, dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methylpropyl ether, methyl butyl ether, diphenyl ether, ditolyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran,dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran,3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane,morpholine, and the like, including substituted derivatives thereof.

Suitable organic carbonyls can include ketones, aldehydes, esters, andamides, either alone or in combination, and illustrative examples caninclude, but are not limited to, acetone, acetophenone, benzophenone,N,N-dimethylformamide, N,N-dimethylacetamide, methyl acetate, ethylacetate, and the like, including substituted derivatives thereof.

Suitable thioethers can include, but are not limited to, dimethylthioether, diethyl thioether, dipropyl thioether, dibutyl thioether,methyl ethyl thioether, methyl propyl thioether, methyl butyl thioether,diphenyl thioether, ditolyl thioether, thiophene, benzothiophene,tetrahydrothiophene, thiane, and the like, including substitutedderivatives thereof.

Suitable nitriles can include, but are not limited to, acetonitrile,propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, andthe like, including substituted derivatives thereof.

Suitable amines can include, but are not limited to, methyl amine, ethylamine, propyl amine, butyl amine, dimethyl amine, diethyl amine,dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine,tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine,tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole,indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole,2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole,2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole,3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3,4-dibutylpyrrole,2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole,3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole,3-ethyl-2,4-dimethylpyrrole, 2,3,4,5-tetramethylpyrrole,2,3,4,5-tetraethylpyrrole, 2,2′-bipyridine,1,8-Diazabicyclo[5.4.0]undec-7-ene, di(2-pyridyl)dimethylsilane,N,N,N′,N′-tetramethylethylenediamine, 1,10-phenanthroline,2,9-dimethyl-1,10-phenanthroline, glyoxal-bis(mesityl)-1,2-diimine andthe like, including substituted derivatives thereof. Suitable amines canbe primary amines, secondary amines, or tertiary amines.

Suitable phosphines and other phosphorus compounds can include, but arenot limited to, trimethylphosphine, triethylphosphine,tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine,diphenylphosphine, ditolylphosphine, triphenylphosphine,tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine,ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine,trimethyl phosphite, triethyl phosphite, tripropyl phosphite,triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite,2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-1,1′-binaphthyl,2-(di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-di-t-butylphosphino-2′-methylbiphenyl,2-(di-t-butylphosphinomethyl)pyridine,2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-(dicyclohexylphosphino)biphenyl,(S)-(+)-(3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a′]dinaphthalen-4-yl)dimethylamine,2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl,1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP),1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)-ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutyl-phosphino)ethane, 1,2-bis(di-t-butyl-phosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane,1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane, 1,3-bis(diphenylphosphino)propane,1,3-bis(di-t-butylphosphino)propane,1,4-bis(diisopropylphosphino)butane, 1,4-bis(diphenylphosphino)butane,2,2′-bis[bis(3,5-dimethylphenyl)phosphino]-4,4′,6,6′-tetramethoxybiphenyl,2,6-bis(di-t-butylphosphinomethyl)pyridine,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,bis(2-dicyclohexylphosphinophenyl)ether,5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole,2-t-butylphosphinomethylpyridine, bis(diphenylphosphino)ferrocene,bis(diphenylphosphino)methane, bis(dicyclohexylphosphino)methane,bis(di-t-butylphosphino)methane, and the like, including substitutedderivatives thereof.

In other aspects, the ligand used to form the metalalactone or thetransition metal precursor compound can be a carbene, for example, aN-heterocyclic carbene (NHC) compound. Representative and non-limitingexamples of suitable N-heterocyclic carbene (NHC) materials include thefollowing:

Illustrative and non-limiting examples of metalalactone complexes(representative nickelalactones) suitable for use as described hereininclude the following compounds (Cy=cyclohexyl, ^(t)Bu=tert-butyl):

The transition metal precursor compounds corresponding to theseillustrative metalalactones are shown below:

Metalalactones can be synthesized according to the following generalreaction scheme (illustrated with nickel as the transition metal;Ni(COD)₂ is bis(1,5-cyclooctadiene)nickel(0)), and according to suitableprocedures well known to those of skill in the art.

Suitable ligands, transition metal precursor compounds, andmetalalactones are not limited solely to those ligands, transition metalprecursor compounds, and metalalactones disclosed herein. Other suitableligands, transition metal precursor compounds, and metalalactones aredescribed, for example, in U.S. Pat. Nos. 7,250,510, 8,642,803, and8,697,909; Journal of Organometallic Chemistry, 1983, 251, C51-C53; Z.Anorg. Allg. Chem., 1989, 577, 111-114; Journal of OrganometallicChemistry, 2004, 689, 2952-2962; Organometallics, 2004, Vol. 23,5252-5259; Chem. Commun., 2006, 2510-2512; Organometallics, 2010, Vol.29, 2199-2202; Chem. Eur. J., 2012, 18, 14017-14025; Organometallics,2013, 32 (7), 2152-2159; and Chem. Eur. J., 2014, Vol. 20, 11,3205-3211; the disclosures of which are incorporated herein by referencein their entirety.

The following references provide information related to the structureand/or activity relationships in the olefin and CO₂ coupling process, asobserved by changes in phenoxide structure, the phosphine ligandstructure, and other ligand structures: Manzini, S.; Huguet, N.; Trapp,O.; Schaub, T. Eur. J. Org. Chem. 2015, 7122; and Al-Ghamdi, M.;Vummaleti, S. V. C.; Falivene, L.; Pasha, F. A.; Beetstra, D. J.;Cavallo, L. Organometallics 2017, 36, 1107-1112. These references areincorporated herein by reference in their entireties.

Generally, the features of the processes disclosed herein (e.g., themetalalactone, the diluent, the anionic polyelectrolyte, theα,β-unsaturated carboxylic acid or salt thereof, the transition metalprecursor compound, the olefin, and the reaction conditions under whichthe α,β-unsaturated carboxylic acid, or a salt thereof, is formed, amongothers) are independently described, and these features can be combinedin any combination to further describe the disclosed processes.

In accordance with an aspect of the present disclosure, a process forperforming a metalalactone elimination reaction is disclosed, in whichthe process forms an α,β-unsaturated carboxylic acid or salt thereof.This process can comprise (or consist essentially of, or consist of):

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.        For example, the suitable reaction conditions may induce a        metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or a salt thereof.        Suitable metalalactones, diluents, and sulfur oxoacid        anion-substituted polyaromatic resin or phosphorus oxoacid        anion-substituted polyaromatic resins (anionic polyelectrolytes)        are disclosed hereinabove. In this process for form the        α,β-unsaturated carboxylic acid or the salt thereof, for        instance, at least a portion of the diluent can comprise the        α,β-unsaturated carboxylic acid, or the salt thereof, that is        formed in step b) of this process.

In accordance with another aspect of the present disclosure, a processfor producing an α,β-unsaturated carboxylic acid, or a salt thereof, isdisclosed. This process can comprise (or consist essentially of, orconsist of):

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations, to provide a reaction mixture comprising an            adduct of the metalalactone compound and sulfur oxoacid            anion-substituted polyaromatic resin or a phosphorus oxoacid            anion-substituted polyaromatic resin; and    -   b) applying reaction conditions to the reaction mixture suitable        to induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or the salt thereof.        In this process for producing an α,β-unsaturated carboxylic acid        or a salt thereof, for instance, at least a portion of the        diluent of the reaction mixture comprising the adduct of the        metalalactone can be removed after step a), and before step b),        of this process. Suitable metalalactones, diluents, and sulfur        oxoacid anion-substituted polyaromatic resins or phosphorus        oxoacid anion-substituted polyaromatic resins (anionic        polyelectrolytes) are disclosed hereinabove.

As discussed further in this disclosure, the above processes can furthercomprise a step of contacting a transition metal precursor compoundcomprising at least one first ligand, an olefin, and carbon dioxide(CO₂) to form the metalalactone compound. That is, at least one ligandof the transition metal precursor compound can be carried over to themetalalactone compound. In further aspects, the above processes canfurther comprise a step of contacting a transition metal precursorcompound comprising at least one first ligand with at least one secondligand, an olefin, and carbon dioxide (CO₂) to form the metalalactonecompound. In this aspect, the ligand set of the metalalactone typicallycomprises the at least one ligand in addition to the metalalactonemoiety. That is, the metalalactone compound can comprise the at leastone first ligand, the at least one second ligand, or a combinationthereof.

In some aspects, the contacting step, step a) of the above processes,can include contacting, in any order, the metalalactone, the diluent,and the sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin, and additionalunrecited materials. In other aspects, the contacting step can consistessentially of, or consist of, the metalalactone, the diluent, and theanionic polyelectrolyte components. Likewise, additional materials orfeatures can be employed in the applying reaction conditions step, stepb) of the above processes, that forms or produces the α,β-unsaturatedcarboxylic acid, or the salt thereof. Further, it is contemplated thatthese processes for producing an α,β-unsaturated carboxylic acid or asalt thereof by a metalalactone elimination reaction can employ morethan one metalalactone and/or more than one anionic polyelectrolyte.Additionally, a mixture or combination of two or more diluents can beemployed.

Any suitable reactor, vessel, or container can be used to contact themetalalactone, diluent, and anionic polyelectrolyte, non-limitingexamples of which can include a flow reactor, a continuous reactor, afixed bed reactor, a moving reactor bed, a stirred bed reactor, abubbling bed reactor, and a stirred tank reactor, including more thanone reactor in series or in parallel, and including any combination ofreactor types and arrangements. In particular aspects consistent withthis disclosure, the metalalactone and the diluent can contact a fixedbed of the anionic polyelectrolyte, for instance, in a suitable vessel,such as in a continuous fixed bed reactor. In other aspects, consistentwith this disclosure, the metalalactone and the diluent can contact amoving bed of the anionic polyelectrolyte, for instance, in a suitablevessel, such as in a moving reactor bed, a stirred bed reactor, or abubbling bed reactor. In further aspects, combinations of more than oneanionic polyelectrolyte can be used, such as a mixed bed of a firstanionic polyelectrolyte and a second anionic polyelectrolyte, orsequential beds of a first anionic polyelectrolyte and a second anionicpolyelectrolyte. In still further aspects, the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin of the contacting step a) isarranged as a fixed bed, a bubbling bed, a moving bed, or a stirred bed.In these and other aspects, the feed stream can flow upward or downwardthrough the fixed bed. For instance, the metalalactone and the diluentcan contact the first anionic polyelectrolyte and then the secondanionic polyelectrolyte in a downward flow orientation, and the reversein an upward flow orientation. In a different aspect, the metalalactoneand the anionic polyelectrolyte can be contacted by mixing or stirringin the diluent, for instance, in a suitable vessel, such as a stirredtank reactor.

Step a) of the process for producing an α,β-unsaturated carboxylic acidor a salt thereof also recites forming an adduct of the metalalactoneand the sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin; wherein thepolyaromatic resin further comprises associated metal cations. Withoutintending to be bound by theory, there is some interaction between themetalalactone and the anionic polyelectrolyte and its associated metalcations that are believed to destabilize the metalalactone for itselimination of the metal acrylate. This interaction can be referred togenerally as an adduct of the metalalactone and the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin (anionic polyelectrolyte) or anadduct of the α,β-unsaturated carboxylic acid with the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin. This adduct can contain all or aportion of the α,β-unsaturated carboxylic acid and can be inclusive ofsalts of the α,β-unsaturated carboxylic acid.

Accordingly, applying reaction conditions to the reaction mixturesuitable to form an α,β-unsaturated carboxylic acid or a salt thereof isintended to reflect any concomitant or subsequent conditions to step a)of the above processes that release the α,β-unsaturated carboxylic acidor a salt thereof from the adduct, regardless of the specific nature ofthe adduct.

For example, in step b) of the process of applying reaction conditionsto the reaction mixture suitable to form an α,β-unsaturated carboxylicacid or a salt thereof, the adduct of the metalalactone and the anionicpolyelectrolyte and its associated metal cations as defined herein issubjected to some chemical or other conditions or treatment to producethe α,β-unsaturated carboxylic acid or its salt. Various methods can beused to liberate the α,β-unsaturated carboxylic acid or its salt, fromthe anionic polyelectrolyte. In one aspect, for instance, the treatingstep can comprise contacting the adduct of the metalalactone and theanionic polyelectrolyte and its associated metal cations with an acid.Representative and non-limiting examples of suitable acids can includeHCl, acetic acid, and the like, as well as combinations thereof. Inanother aspect, the treating step can comprise contacting the adduct ofthe metalalactone and the anionic polyelectrolyte and its associatedmetal cations with a base.

Representative and non-limiting examples of suitable bases can includecarbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃), hydroxides (e.g., Mg(OH)₂,Na(OH), alkoxides (e.g., Al(O^(i)Pr)₃, Na(O^(t)Bu), Mg(OEt)₂), and thelike, as well as combinations thereof (^(i)Pr=isopropyl,^(t)Bu=tert-butyl, Et=ethyl). In yet another aspect, the treating stepcan comprise contacting the adduct of the metalalactone and the anionicpolyelectrolyte and its associated metal cations with a suitablesolvent. Representative and non-limiting examples of suitable solventscan include carbonyl-containing solvents such as ketones, esters,amides, etc. (e.g., acetone, ethyl acetate, N,N-dimethylformamide, etc.,as described herein above), alcohol solvents, water, and the like, aswell as combinations thereof.

In still another aspect, the treating step can comprise heating theadduct of the metalalactone and the anionic polyelectrolyte and itsassociated metal cations to any suitable temperature. This temperaturecan be in a range, for example, from 50 to 1000° C., from 100 to 800°C., from 150 to 600° C., from 250 to 1000° C., from 250° C. to 550° C.,or from 150° C. to 500° C. The duration of this heating step is notlimited to any particular period of time, as long of the period of timeis sufficient to liberate the α,β-unsaturated carboxylic acid from theanionic polyelectrolyte. As those of skill in the art recognize, theappropriate treating step depends upon several factors, such as theparticular diluent used in the process, and the particular anionicpolyelectrolyte used in the process, amongst other considerations. Onefurther treatment step can comprise, for example, a workup step withadditional olefin to displace an alkene-nickel bound acrylate.

In these processes for performing a metalalactone elimination reactionand for producing an α,β-unsaturated carboxylic acid (or a saltthereof), additional process steps can be conducted before, during,and/or after any of the steps described herein. As an example, theseprocesses can further comprise a step (e.g., prior to step a)) ofcontacting a transition metal precursor compound with an olefin andcarbon dioxide to form the metalalactone. Transition metal precursorcompound are described hereinabove. Illustrative and non-limitingexamples of suitable olefins can include ethylene, propylene, butene(e.g., 1-butene), pentene, hexene (e.g., 1-hexene), heptane, octene(e.g., 1-octene), and styrene and the like, as well as combinationsthereof.

In accordance with another aspect of the present disclosure, a processfor forming an α,β-unsaturated carboxylic acid, or a salt thereof,involves coupling an olefin with carbon dioxide, in the present of atransition metal precursor compound. For example, this process or methodcan comprise (or consist essentially of, or consist of):

-   -   a) contacting in any order        -   1) a transition metal precursor compound comprising at least            one first ligand;        -   2) optionally, at least one second ligand;        -   3) an olefin;        -   4) carbon dioxide (CO₂);        -   5) a diluent; and        -   6) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.

In aspects of this process that utilizes a transition metal precursorcompound comprising at least one first ligand, the olefin can beethylene, and the step of contacting a transition metal precursorcompound with an olefin and carbon dioxide (CO₂) can be conducted usingany suitable pressure of ethylene, or any pressure of ethylene disclosedherein, e.g., from 10 psig (70 KPa) to 1,000 psig (6,895 KPa), from 25psig (172 KPa) to 500 psig (3,447 KPa), or from 50 psig (345 KPa) to 300psig (2,068 KPa), and the like. Further, the olefin can be ethylene, andthe step of contacting a transition metal precursor compound with anolefin and carbon dioxide (CO₂) can be conducted using a constantaddition of the olefin, a constant addition of carbon dioxide, or aconstant addition of both the olefin and carbon dioxide, to provide thereaction mixture. By way of example, in a process wherein the ethyleneand carbon dioxide (CO₂) are constantly added, the process can utilizean ethylene:CO₂ molar ratio of from 5:1 to 1:5, from 3:1 to 1:3, from2:1 to 1:2, or about 1:1, to provide the reaction mixture.

According to a further aspect of the above process that utilizes atransition metal precursor compound, the process can include the step ofcontacting a transition metal precursor compound with an olefin andcarbon dioxide (CO₂) conducted using any suitable pressure of CO₂, orany pressure of CO₂ disclosed herein, e.g., from 20 psig (138 KPa) to2,000 psig (13,790 KPa), from 50 psig (345 KPa) to 750 psig (5,171 KPa),or from 100 psig (689 KPa) to 300 psig (2,068 KPa), and the like. In anyof the processes disclosed herein, the processes can further comprise astep of monitoring the concentration of at least one reaction mixturecomponent, at least one elimination reaction product, or a combinationthereof, for any reason, such as to adjust process parameters in realtime, to determine extent or reaction, or to stop the reaction at thedesired point.

As illustrated, this process that utilizes a transition metal precursorcompound comprising at least one first ligand includes one aspect inwhich no second ligand is employed in the contacting step, and anotheraspect in which a second ligand is used in the contacting step. That is,one aspect involves the contacting step of the process comprisingcontacting the transition metal precursor compound comprising at leastone first ligand with the at least one second ligand. The order ofcontacting can be varied. For example, the contacting step of theprocess disclosed above can comprise contacting 1) the transition metalprecursor compound comprising at least one first ligand with 2) the atleast one second ligand to form a pre-contacted mixture, followed bycontacting the pre-contacted mixture with the remaining components 3)-6)in any order to provide the reaction mixture.

Further embodiments related to the order of contacting, for example, thecontacting step can include or comprise contacting the metalalactone,the diluent, and the sulfur oxoacid anion-substituted polyaromatic resinor the phosphorus oxoacid anion-substituted polyaromatic resin (anionicpolyelectrolyte) in any order. The contacting step can also comprisecontacting the metalalactone and the diluent to form a first mixture,followed by contacting the first mixture with the anionicpolyelectrolyte to form the reaction mixture. In a further aspect, thecontacting step can comprise contacting the diluent and the anionicpolyelectrolyte to form a first mixture, followed by contacting thefirst mixture with the metalalactone to form the reaction mixture. Inyet a further aspect, the contacting step of the process furthercomprises contacting any number of additives, for example, additivesthat can be selected from an acid, a base, or a reductant.

Suitable transition metal precursors, first ligands, second ligands,olefins, diluents, anionic polyelectrolytes with associated metalcations are disclosed hereinabove. In some aspects, the contactingstep—step a)—of this process can include contacting, in any order, thetransition metal-ligand, the olefin, the diluent, the anionicpolyelectrolyte, and carbon dioxide, and additional unrecited materials.In other aspects, the contacting step can consist essentially of, orconsist of, contacting, in any order, the transition metal-ligand, theolefin, the diluent, the anionic polyelectrolyte, and carbon dioxide.Likewise, additional materials or features can be employed in theforming step of step b) of this process. Further, it is contemplatedthat this processes for producing an α,β-unsaturated carboxylic acid, ora salt thereof, can employ more than one transition metal-ligand complexand/or more than one anionic polyelectrolyte if desired and/or more thanone olefin. Additionally, a mixture or combination of two or morediluents can be employed.

As above, any suitable reactor, vessel, or container can be used tocontact the transition metal precursors, first ligands, second ligands,olefin, diluent, anionic polyelectrolyte, and carbon dioxide, whetherusing a fixed bed of the anionic polyelectrolyte, a stirred tank forcontacting (or mixing), or some other reactor configuration and process.While not wishing to be bound by the following theory, a proposed andillustrative reaction scheme for this process is provided below.

Independently, the contacting and forming steps of any of the processesdisclosed herein (i.e., for performing a metalalactone eliminationreaction, for producing an α,β-unsaturated carboxylic acid, or a saltthereof), can be conducted at a variety of temperatures, pressures, andtime periods. For instance, the temperature at which the components instep a) are initially contacted can be the same as, or different from,the temperature at which the forming step b) is performed. As anillustrative example, in the contacting step, the components can becontacted initially at temperature T1 and, after this initial combining,the temperature can be increased to a temperature T2 for the formingstep (e.g., to form the α,β-unsaturated carboxylic acid, or the saltthereof). Likewise, the pressure can be different in the contacting stepand the forming step. Often, the time period in the contacting step canbe referred to as the contact time, while the time period in formingstep can be referred to as the reaction time. The contact time and thereaction time can be, and often are, different.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein can be conducted at a temperature in a rangefrom 0° C. to 250° C.; alternatively, from 20° C. to 200° C.;alternatively, from 0° C. to 95° C.; alternatively, from 10° C. to 75°C.; alternatively, from 10° C. to 50° C.; or alternatively, from 15° C.to 70° C. In these and other aspects, after the initial contacting, thetemperature can be changed, if desired, to another temperature for theforming step. These temperature ranges also are meant to encompasscircumstances where the contacting step and/or the forming step can beconducted at a series of different temperatures, instead of at a singlefixed temperature, falling within the respective ranges.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein can be conducted at a pressure in a rangefrom 5 (34 KPa) to 10,000 psig (68,948 KPa), such as, for example, from5 psig (34 KPa) to 2500 psig (17,237 KPa). In some aspects, the pressurecan be in a range from 5 psig (34 KPa) to 500 psig (3,447 KPa);alternatively, from 25 psig (172 KPa) to 3000 psig (20,684 KPa);alternatively, from 45 psig (310 KPa) to 1000 psig (6,895 KPa); oralternatively, from 50 psig (345 KPa) to 250 psig (1,724 KPa).

The contacting step of the processes is not limited to any particularduration of time. That is, the respective components can be initiallycontacted rapidly, or over a longer period of time, before commencingthe forming step. Hence, the contacting step can be conducted, forexample, in a time period ranging from as little as 1-30 seconds to aslong as 1-12 hours, or more. In non-continuous or batch operations, theappropriate reaction time for the forming step can depend upon, forexample, the reaction temperature, the reaction pressure, and the ratiosof the respective components in the contacting step, among othervariables. Generally, however, the forming step can occur over a timeperiod that can be in a range from 1 minute to 96 hours, such as, forexample, from 2 minutes to 96 hours, from 5 minutes to 72 hours, from 10minutes to 72 hours, or from 15 minutes to 48 hours.

If the process employed is a continuous process, then themetalalactone/anionic electrolyte catalyst contact/reaction time (or thetransition metal precursors, first ligands, second ligands, olefin,diluent, anionic polyelectrolyte, and carbon dioxide contact/reactiontime) can be expressed in terms of weight hourly space velocity(WHSV)—the ratio of the weight of the metalalactone (or the solutioncontinuing the transition metal precursors, first ligands, secondligands, olefin, diluent, anionic polyelectrolyte, and carbon dioxide)which comes in contact with a given weight of anionic electrolyte perunit time (for example, hr⁻¹). While not limited thereto, the WHSVemployed, based on the amount of the anionic electrolyte, can be in arange from 0.05 to 100 hr⁻¹, from 0.05 to 50 hr⁻¹, from 0.075 to 50hr⁻¹, from 0.1 to 25 hr⁻¹, from 0.5 to 10 hr⁻¹, from 1 to 25 hr⁻¹, orfrom 1 to 5 hr⁻¹.

In the processes disclosed herein, the molar yield of theα,β-unsaturated carboxylic acid, or the salt thereof), based on themetalalactone (or the metal precursors) is at least 2%, and more oftencan be at least 5%, at least 10%, or at least 15%. In particular aspectsof this disclosure, the molar yield can be at least 18%, at least 20%,at least 25%, at least 35%, at least 50%, at least 60%, at least 75%, orat least 85%, or at least 90%, or at least 95%, or at least 100%. Thatis, catalytic formation of the α,β-unsaturated carboxylic acid or thesalt thereof can be effected with the disclosed system. For example, themolar yield of the α,β-unsaturated carboxylic acid, or the salt thereof,based on the metalalactone or based on the transition metal precursorcompound can be at least 20%, at least 40%, at least 60%, at least 80%,at least 100%, at least 120%, at least 140%, at least 160%, at least180%, at least 200%, at least 250%, at least 300%, at least 350%, atleast 400%, at least 450%, or at least 500%.

The specific α,β-unsaturated carboxylic acid (or salt thereof) that canbe formed or produced using the processes of this disclosure is notparticularly limited. Illustrative and non-limiting examples of theα,β-unsaturated carboxylic acid can include acrylic acid, methacrylicacid, 2-ethylacrylic acid, cinnamic acid, and the like, as well ascombinations thereof. Illustrative and non-limiting examples of the saltof the α,β-unsaturated carboxylic acid can include sodium acrylate,potassium acrylate, magnesium acrylate, sodium (meth)acrylate, and thelike, as well as combinations thereof.

Once formed, the α,β-unsaturated carboxylic acid (or salt thereof) canbe purified and/or isolated and/or separated using suitable techniqueswhich can include, but are not limited to, evaporation, distillation,chromatography, crystallization, extraction, washing, decanting,filtering, drying, and the like, including combinations of more than oneof these techniques. In an aspect, the process can for performing ametalalactone elimination reaction (or the process for producing anα,β-unsaturated carboxylic acid, or a salt thereof) can further comprisea step of separating or isolating the α,β-unsaturated carboxylic acid(or salt thereof) from other components, e.g., the diluent, the anionicelectrolyte, and the like.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

General Considerations

Unless otherwise noted, all operations were performed under purifiednitrogen or vacuum using standard Schlenk or glovebox techniques.Toluene (Honeywell) and tetrahydrofuran (Aldrich) was degassed and driedover activated 4 Å molecular sieves under nitrogen. Sodiumtert-butoxide, potassium tert-butoxide, poly(4-vinylbenzenesulfonicacid) and poly(4-vinylbenzenephosphonic acid), were prepared bypublished methods or purchased from Sigma-Aldrich and used as received.

Phenol/formaldehyde resin was purchased as hollow beads (˜5-127 μm) fromPolysciences, Inc. Bis(1,5-cyclooctadiene)nickel(0) and1,2-bis(dicyclohexylphosphino)ethane were purchased from Strem and wereused as received. (TMEDA)Ni(CH₂CH₂CO₂) was prepared according toliterature procedures (Fischer, R; Nestler, B., and Schutz, H. Z. anorg.allg. Chem. 577 (1989) 111-114).

Preparation of Compounds

Sodium Phenol/Formaldehyde Resin.

Phenolic resin (phenol/formaldehyde resin) was suspended in a solutionof sodium hydroxide in either water or methanol and stirred at 55° C.overnight prior to filtration, and subsequently washed with copiousamounts of the solvent in which it was treated. The solid was then driedunder vacuum prior to storage under nitrogen.

Preparation of Functionalized Polyaromatic Resins.

The sulfur oxoacid anion-substituted polyaromatic resins and/or aphosphorus oxoacid anion-substituted polyaromatic resins can be preparedas disclosed hereinabove. For example, sulfonation and phosphonation ofaromatic materials can be performed by a treatment of the resin with theappropriate acid under various temperatures, concentrations, and diluentconditions. These oxoacid installations can be accelerated andselectively placed when sulfonated/halogenated aromatic substratescatalytically coupled with sulfonate/phosphonate precursors. Forexample, alkyl phosphites can be installed and subsequently hydrolyzedwhen a cross coupling catalyst such as nickel(II) chloride or bromide isemployed. Sulfination of an aryl group can occur by reducing theappropriate sulfonyl chloride (prepared from thionyl chloride treatmentof the sulfonate) with a reagent such as zinc dust, and also can occurusing Grignard reagents, dialkyl zinc compounds, hydrogen/palladiumcatalyst systems, sodium/mercury amalgam, and other electron sources.Various approaches are described in Chem. Rev., 1951, 48 (1), pp 69-124,which is incorporated herein by reference in its entirety.Thiosulfination and thiosulfonation can proceed from a variety ofroutes. For example, one utilized protocol involves the oxidativecleavage of disulfide linkages (introduced through sulfur-inducedcrosslinking of a polyaromatic microstructure), which can be performedusing oxidation treatments of various strengths (depending on whetherthiosulfinate or thiosulfonate functionality is desired) includingmCPBA, hydrogen peroxide, or sulfuryl chloride. Thionyl chloridetreatment of such linkages can produce sulfinyl chloride moieties whichcan be further treated with sodium sulfide or acid to afford the desiredmaterial. Subsequent base (e.g. sodium hydroxide or sodium chloride)treatment can be used to generate the metal-stabilized anionicpolyelectrolyte. Various approaches to these materials can be found in,for example, Fischmann, A. J.; Spiccia, L. Dalton Trans. 2011, 40,12310, which is incorporated herein by reference in its entirety.

Examples 1-20

Experimental Procedure for Ethylene/Carbon Dioxide Coupling

The ethylene/carbon dioxide reaction of these examples is set out inScheme 4 below, and specific reagents, reaction conditions, and yieldsare set out in Table 1.

A 1-liter autoclave pressure reactor is charged with solvent followed bya combined mixture of Ni(COD)₂ (0.10 mmol),bis(dicyclohexylphosphino)ethane (0.11 mmol), andpoly(4-vinylbenzenesulfonic acid) or poly(4-vinylbenzenephosphonic acid)(1.00 g) in 10 mL of solvent. The reactor is set to 50° C., pressurizedwith ethylene at the desired level, and equilibrated for 5-10 minutes(min) prior to being pressurized and equilibrated with carbon dioxide.The reactor is set to 100° C. and is stirred for 6 hours. After thisreaction time, and after cooling to ambient temperature, the reactor isslowly vented and the mixture is collected. The solvent is removed invacuo and the residue is stirred in 10-20 mL of deuterium oxide for 30min prior to the addition of a sorbic acid/acetone-d₆ solution. Themixture can then be filtered and analyzed by NMR (sorbic acid is used asthe internal standard) for acrylate yield determination.

TABLE 1 Ethylene and carbon dioxide coupling examples [Solvent] [C₂H₄][CO₂] Example X Solvent (mL) (psi (KPa)) (psi (KPa) 1 SO₂(ONa) Toluene300 100 150 (689) (1,034) 2 PO(ONa)₂ Toluene 300 100 150 (689) (1,034) 3SO(ONa) Toluene 300 100 150 (689) (1,034) 4 S(S)O(ONa) Toluene 300 100150 (689) (1,034) 5 SS(ONa) Toluene 300 100 150 (689) (1,034) 6 SO₂(ONa)Toluene 100 150 300 (1,034)   (2,068) 7 PO(ONa)₂ Toluene 100 150 300(1,034)   (2,068) 8 SO(ONa) Toluene 100 150 300 (1,034)   (2,068) 9S(S)O(ONa) Toluene 100 150 300 (1,034)   (2,068) 10 SS(ONa) Toluene 100150 300 (1,034)   (2,068) 11 SO₂(ONa) THF 300  75 300 (517) (2,068) 12PO(ONa)₂ THF 300  75 300 (517) (2,068) 13 SO(ONa) THF 300  75 300 (517)(2,068) 14 S(S)O(ONa) THF 300  75 300 (517) (2,068) 15 SS(ONa) THF 300 75 300 (517) (2,068) 16 SO₂(ONa) Toluene 50 100 250 (689) (1,723) 17PO(ONa)₂ Toluene 50 100 250 (689) (1,723) 18 SO(ONa) Toluene 50 100 250(689) (1,723) 19 S(S)O(ONa) Toluene 50 100 250 (689) (1,723) 20 SS(ONa)Toluene 50 100 250 (689) (1,723)

Additional resin types that can be employed according to the reactionScheme 4 and this disclosure are illustrated in the following reactionScheme 5, and reaction parameters such as disclosed in the table abovecan be utilized in this reaction scheme as well.

Examples 21-37

Experimental Procedure for Nickelalactone Conversion to Acrylate

To study the elimination step of the disclosed process, the efficienciesof various alkoxides or aryloxides for the conversion of adiphosphine-stabilized nickelalactone to acrylic acid were assessed.Specifically, the following experiments show the efficiencies of sodiumand potassium (4-vinylphenoxide) for the conversion of an in situprepared diphosphine-stabilized nickelalactone, and the data werecompared to the conversion using molecular sodium tert-butoxide foracrylate formation from the analogous nickelalactones. The metalalactoneto acrylate conversion reaction of these examples is set out in thescheme below, with exemplary sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resins shown. Additional sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resins are set out in Table 2, along with suitablesolvents, that can be used in the process of Scheme 6.

In a 10 mL vial, (TMEDA)Ni(CH₂CH₂CO₂) (0.018 mmol),bis(dicyclohexylphosphino)-ethane (0.018 mmol), the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin, and solvent (5 mL) is combined andstirred at 60° C. for 30-60 min. Following removal of solvent, the solidresidue is taken up in D₂O (3-5 mL) for 30 min and filtered. An aliquotof a prepared sorbic acid/acetone-d₆ solution can be added fordetermination of acrylic acid yield by NMR.

TABLE 2 Exemplary sulfur and phosphorus oxoacid anion-substitutedpolymers and copolymers Example Polyaromatic Resin Solvent 21 Sodiumpoly(4-vinylbenzenesulfonate) Toluene, THF 22 Sodiumpoly(4-vinylbenzenephosphonate) Toluene, THF 23 Sodiumpoly(4-vinylbenzenesulfinate) Toluene, THF 24 Sodiumpoly(4-vinylbenzenethiosulfonate) Toluene, THF 25 Sodiumpoly(4-vinylbenzenethiosulfinate) Toluene, THF 26 Sodiumpoly(4-vinylbenzenesulfonate-co- Toluene, THF methyl(meth)acrylate) 27Sodium poly(4-vinylbenzenephosphonate- Toluene, THFco-methyl(meth)acrylate) 28 Sodium poly(4-vinylbenzenesulfinate-co-Toluene, THF methyl(meth)acrylate) 29 Sodiumpoly(4-vinylbenzenethiosulfonate- Toluene, THF co-methyl(meth)acrylate)30 Sodium poly(4-vinylbenzenethiosulfinate- Toluene, THFco-methyl(meth)acrylate) 31 Sodium poly(4-vinylbenzenesulfonate-co-Toluene, THF divinylbenzene) 32 Sodium poly(4-vinylbenzenephosphonate-Toluene, THF co-divinylbenzene) 33 Sodiumpoly(4-vinylbenzenesulfinate-co- Toluene, THF divinylbenzene) 34 Sodiumpoly(4-vinylbenzenethiosulfonate- Toluene, THF co-divinylbenzene) 35Sodium poly(4-vinylbenzenethiosulfinate- Toluene, THF co-divinylbenzene)36 AMBERLITE ® IR120 Na Toluene, THF 37 AMBERLYST ® Toluene, THF

Additional resin types that can be employed according to the reactionScheme 6 and this disclosure are illustrated in the following reactionScheme 7, and reaction parameters such as disclosed in the table abovecan be utilized in this reaction scheme as well.

Examples 38-39

Commercial Sulfur Oxoacid Anion-Substituted Resins as StoichiometricCo-Catalysts in Olefin/Carbon Dioxide Conversion to α,β-UnsaturatedCarboxylates and their Regeneration

Because various sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resins were foundto be suitable promoters and sources of cations in the conversion ofolefin and carbon dioxide-derived nickelalactone intermediates, anevaluation of their crosslinked analogues was undertaken. It wasbelieved that these crosslinked polyaromatic resins would besufficiently insoluble in many commercial diluents and be applicable asa polymeric promoters and cation sources in a fixed bed and/or columnreactor setting. This method further allows for the potentialregeneration of the spent solid co-catalyst in both aqueous (forexample, sodium hydroxide in water) and/or organic media (for example,sodium alkoxide in toluene) and using sodium chloride as a sodiumsource.

In these examples, commercially available sodium form of AMBERLITE®, acrosslinked polystyrene sulfonate resin, was used in the couplingreaction of CO₂ and ethylene, and was found to be effective as aheterogeneous solid activator (co-catalyst) in the process. TheAMBERLITE® used is described as a styrene divinylbenzene sulfonated.Scheme 8 illustrates the conversion reaction of an olefin and carbondioxide-derived nickelalactone intermediate that was undertaken toevaluate some crosslinked polyaromatic e analogues. Reaction conditionsfor Scheme 8 are: 0.10 mmol [Ni], 0.11 mmol diphosphine ligand, 500 mLof toluene, 1.0 g of sodium-treated, crosslinked polyaromatic resin(solid activator). The reactor was equilibrated to 150 psi of ethylenefollowed by 300 psi of carbon dioxide prior to heating. The yieldreported in Table 3 was determined by ¹H NMR spectroscopy in aD₂O/(CD₃)₂CO mixture relative to a sorbic acid standard.

TABLE 3 Coupling reactions using commercial resins Acrylate ExampleSolid Activator Resin Type Yield (%) 38 AMBERLITE ® Sulfonated, dried^(A) 6.7 120 Na+ 39 AMBERLITE ® Sulfonated, not dried ^(B) Not detected120 Na+ ^(A) Resin was dried in the reactor under a nitrogen stream at100° C. prior to the reaction. ^(B) Resin was used without furthertreatment.

Example 40

Polymeric Stationary Phases for Catalytic Acrylate Formation

The present disclosure also provides for using polymeric stationaryphases comprising the sulfur oxoacid anion-substituted polyaromaticresin or the phosphorus oxoacid anion-substituted polyaromatic resins,such as functionalized polystyrenes or phenol-formaldehyde type resins,in a column or other suitable solid state configuration, in whichformation of the acrylate from a metalalactone (such as anickelalactone) in a mobile phase can be effected.

FIG. 1 illustrates one way in which a polymeric stationary phasecatalyst column can be configured, in which the coupling reaction andelution of the metal acrylate from the column can be carried out. Asshown, a sulfonated, a phosphonated, a sulfinated, a thiosulfonated, ora thiosulfinated polystyrene or styrene-divinylbenzene copolymer can beused according to FIG. 1. This method can provide both easier separationof acrylate from other materials and ease of regeneration of thepolymeric support materials to its salt form, such as sodiumpoly(4-vinylphenoxide).

Example 41

Crosslinked Polyaromatic Resin Co-Catalysts in Olefin/Carbon DioxideConversion to α,β-Unsaturated Carboxylates, Using Co-Monomers

In this example, co-monomer phenol compounds are used together withformaldehyde to prepare the crosslinked polyaromatic resins for use asdescribed according to the disclosure. The resin was prepared using theco-monomer combination of resorcinol (m-dihydroxybenzene) and2-fluorophenol monomer with formaldehyde, and the resulting resin wassodium-treated (NaOH, dissolved in water or alcohol) to generate theanionic polyelectrolyte, according to equation (4).

Once prepared, the resulting polyaromatic resin can be functionalized,for example, with sulfonic acid groups, phosphonic acid groups, sulfinicacid groups, thiosulfonic acid groups, and/or thiosulfinic acid groupsand treated with sodium hydroxide or another base to form thecorresponding s a sulfonated, a phosphonated, a sulfinated, athiosulfonated, or a thiosulfinated materials, which can promotenickelalactone scission.

In an aspect, such crosslinked resins can be converted into a porouscarbonaceous material upon the pyrolysis of the phenol formaldehyderesin. These pyrolyzed materials, in turn, can be functionalized byvarious treatments to provide sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin materials. For example, pyrolyzed materials may besulfonated by sulfuric acid treatment. Similarly, the pyrolyzedmaterials may be sulfinated by SO₂ treatment, sulfonic acid treatment,or sulfinic acid treatment of the porous carbonaceous material derivedfrom the pyrolysis. The thiosulfonated polyaromatic resin can generatedby, for example, thiosulfonic acid treatment of this porous carbonaceousmaterial. The phosphonated polyaromatic resin also can be formed byaromatic substitution with a chlorinated phosphine, followed byalcoholic or aqueous workup, of a crosslinked polystyrene or a porouscarbonaceous material derived from the pyrolysis of a phenolformaldehyde resin.

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other aspects of the invention caninclude, but are not limited to, the following aspects. Many aspects aredescribed as “comprising” certain components or steps, butalternatively, can “consist essentially of” or “consist of” thosecomponents or steps unless specifically stated otherwise.

Aspect 1. A process for forming an α,β-unsaturated carboxylic acid orsalt thereof, the process comprising

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.

Aspect 2. A process for forming an α,β-unsaturated carboxylic acid or asalt thereof, the process comprising:

-   -   a) contacting        -   1) a metalalactone compound;        -   2) a diluent; and        -   3) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations, to provide a reaction mixture comprising an            adduct of the metalalactone and sulfur oxoacid            anion-substituted polyaromatic resin or a phosphorus oxoacid            anion-substituted polyaromatic resin; and    -   b) applying reaction conditions to the reaction mixture suitable        to induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or the salt thereof.

Aspect 3. A process for forming an α,β-unsaturated carboxylic acid or asalt thereof, the process comprising:

-   -   a) contacting in any order        -   1) a transition metal precursor compound comprising at least            one first ligand;        -   2) optionally, at least one second ligand;        -   3) an olefin;        -   4) carbon dioxide (CO₂);    -   5) a diluent; and    -   6) a sulfur oxoacid anion-substituted polyaromatic resin or a        phosphorus oxoacid anion-substituted polyaromatic resin; wherein        the polyaromatic resin further comprises associated metal        cations to provide a reaction mixture; and    -   b) applying reaction conditions to the reaction mixture suitable        to form the α,β-unsaturated carboxylic acid or the salt thereof.

Aspect 4. The process according to any one of Aspects 1-3, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin comprises a sulfonatedpolyaromatic resin, a phosphonated polyaromatic resin, a sulfinatedpolyaromatic resin, a thiosulfonated polyaromatic resin, or athiosulfinated polyaromatic resin.

Aspect 5. The process according to any one of Aspects 1-3, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin comprises a sulfonated, aphosphonated, a sulfinated, a thiosulfonated, or a thiosulfinatedstyrene polymer or copolymer.

Aspect 6. The process according to any one of Aspects 1-3, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin comprises a sulfonated, aphosphonated, a sulfinated, a thiosulfonated, or a thiosulfinatedstyrene-divinylarene copolymer.

Aspect 7. The process according to any one of Aspects 1-3, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin comprises a sulfonated, aphosphonated, a sulfinated, a thiosulfonated, or a thiosulfinatedstyrene-divinylbenzene copolymer.

Aspect 8. The process according to any one of Aspects 1-3, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin comprises a macroreticularsulfonated, a macroreticular phosphonated, a macroreticular sulfinated,a macroreticular thiosulfonated, or a macroreticular thiosulfinatedstyrene-divinylbenzene copolymer.

Aspect 9. The process according to any one of Aspects 1-7, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin has an average particlesize from about 0.1 mm to about 1.0 mm.

Aspect 10. The process according to any one of Aspects 1-7, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin has an average particlesize from about 0.50 mm to about 0.80 mm.

Aspect 11. The process according to any one of Aspects 1-9, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin is insoluble in the diluentor the reaction mixture.

Aspect 12. The process according to any one of Aspects 1-9, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin is soluble in the diluentor the reaction mixture.

Aspect 13. The process according to any one of Aspects 1 or 4-11,wherein the reaction mixture comprises an adduct of the metalalactoneand the sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin.

Aspect 14. The process according to any one of Aspects 1-12, wherein theassociated metal cations are selected from a Group 1, 2, 12 or 13 metal.

Aspect 15. The process according to any one of Aspects 1-13, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin is macroporous, having anaverage pore diameter greater than about 50 nm.

Aspect 16. The process according to any one of Aspects 1-13, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin has an average porediameter from about 50 nm to about 250 nm.

Aspect 17. The process according to any one of Aspects 1-15, wherein theassociated metal cations comprise any suitable Lewis acidic metal cationor any Lewis acidic metal cation disclosed herein.

Aspect 18. The process according to any one of Aspects 1-15, wherein theassociated metal cations are an alkali metal, an alkaline earth metal,or a combination thereof.

Aspect 19. The process according to any one of Aspects 1-15, wherein theassociated metal cations are lithium, sodium, potassium, rubidium,cesium, magnesium, calcium, strontium, barium, zinc, aluminum, orgallium.

Aspect 20. The process according to any one of Aspects 1-15, wherein theassociated metal cations are sodium or potassium.

Aspect 21. The process according to any one of Aspects 1-15, wherein thewherein the sulfur oxoacid anion-substituted polyaromatic resin is anAMBERLITE® or AMBERLYST® resin.

Aspect 22. The process according to any one of Aspects 1-19, wherein thesulfonated polyaromatic resin is generated by sulfuric acid treatment ofa crosslinked polystyrene or a porous carbonaceous material derived fromthe pyrolysis of a phenol formaldehyde resin.

Aspect 23. The process according to any one of Aspects 1-19, wherein thesulfur oxoacid anion-substituted polyaromatic resin is generated by SO₂treatment (e.g. SO₂(aq)), sulfonic acid treatment, sulfinic acidtreatment, thiosulfonic acid treatment, or thiosulfinic acid treatmentof a crosslinked polystyrene or a porous carbonaceous material derivedfrom the pyrolysis of a phenol formaldehyde resin.

Aspect 24. The process according to any one of Aspects 1-19, wherein thephosphonated polyaromatic resin is generated by aromatic substitutionwith a chlorinated phosphine, followed by alcoholic or aqueous workup,of a crosslinked polystyrene or a porous carbonaceous material derivedfrom the pyrolysis of a phenol formaldehyde resin.

Aspect 25. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable non-protic solvent, or any non-proticsolvent disclosed herein.

Aspect 26. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable weakly coordinating or non-coordinatingsolvent, or any weakly coordinating or non-coordinating solventdisclosed herein.

Aspect 27. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable aromatic hydrocarbon solvent, or anyaromatic hydrocarbon solvent disclosed herein, e.g., benzene, xylene,toluene, etc.

Aspect 28. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable ether solvent, or any ether solventdisclosed herein, e.g., THF, dimethyl ether, diethyl ether, dibutylether, etc.

Aspect 29. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable carbonyl-containing solvent, or anycarbonyl-containing solvent disclosed herein, e.g., ketones, esters,amides, etc. (e.g., acetone, ethyl acetate, N,N-dimethylformamide,etc.).

Aspect 30. The process according to any one of Aspects 1-22, wherein thediluent comprises any suitable halogenated aromatic hydrocarbon solvent,or any halogenated aromatic hydrocarbon solvent disclosed herein, e.g.,chlorobenzene, dichlorobenzene, etc.

Aspect 31. The process according to any one of Aspects 1-22, wherein thediluent comprises THF, 2,5-Me₂THF, methanol, acetone, toluene,chlorobenzene, pyridine, or a combination thereof.

Aspect 32. The process according to any one of Aspects 1-29, wherein thediluent comprises carbon dioxide.

Aspect 33. The process according to any one of Aspects 1-30, wherein atleast a portion of the diluent comprises the α,β-unsaturated carboxylicacid or the salt thereof, formed in the process.

Aspect 34. The process according to any one of Aspects 1-31, wherein thecontacting step further comprises contacting an additive selected froman acid, a base, or a reductant.

Aspect 35. The process according to any one of Aspects 3-31, wherein thecontacting step comprises contacting the transition metal precursorcompound comprising at least one first ligand with the at least onesecond ligand.

Aspect 36. The process according to any one of Aspects 3-31, wherein thecontacting step comprises contacting 1) the transition metal precursorcompound comprising at least one first ligand with 2) the at least onesecond ligand to form a pre-contacted mixture, followed by contactingthe pre-contacted mixture with the remaining components 3)-6) in anyorder to provide the reaction mixture.

Aspect 37. The process according to any one of Aspects 1-2 or 4-31,wherein the contacting step comprises contacting the metalalactone, thediluent, and the sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resin in anyorder.

Aspect 38. The process according to any one of Aspects 1-2 or 4-31,wherein the contacting step comprises contacting the metalalactone andthe diluent to form a first mixture, followed by contacting the firstmixture with the sulfur oxoacid anion-substituted polyaromatic resin orthe phosphorus oxoacid anion-substituted polyaromatic resin to form thereaction mixture.

Aspect 39. The process according to any one of Aspects 1-2 or 4-31,wherein the contacting step comprises contacting the diluent and thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin to form a first mixture,followed by contacting the first mixture with the metalalactone to formthe reaction mixture.

Aspect 40. The process according to any one of Aspects 1-31, wherein thereaction conditions suitable to form the α,β-unsaturated carboxylic acidor the salt thereof comprise contacting the reaction mixture with anysuitable acid, or any acid disclosed herein, e.g., HCl, acetic acid,etc.

Aspect 41. The process according to any one of Aspects 1-31, wherein thereaction conditions suitable to form the α,β-unsaturated carboxylic acidor the salt thereof comprise contacting the reaction mixture with anysuitable solvent, or any solvent disclosed herein, e.g.,carbonyl-containing solvents such as ketones, esters, amides, etc.(e.g., acetone, ethyl acetate, N,N-dimethylformamide), alcohols, water,etc.

Aspect 42. The process according to any one of Aspects 1-39, wherein thereaction conditions suitable to form the α,β-unsaturated carboxylic acidor the salt thereof comprise heating the reaction mixture to anysuitable temperature, or a temperature in any range disclosed herein,e.g., from 50 to 1000° C., from 100 to 800° C., from 150 to 600° C.,from 250 to 550° C., etc.

Aspect 43. The process according to any one of Aspects 1-40, wherein themolar yield of the α,β-unsaturated carboxylic acid, or the salt thereof,based on the metalalactone (in those preceding Aspects comprising ametalalactone) or based on the transition metal precursor compound (inthose preceding Aspects comprising a transition metal precursorcompound) is in any range disclosed herein, e.g., at least 20%, at least40%, at least 60%, at least 80%, at least 100%, at least 120%, at least140%, at least 160%, at least 180%, at least 200%, at least 250%, atleast 300%, at least 350%, at least 400%, at least 450%, or at least500%, etc.

Aspect 44. The process according to any one of Aspects 1-41, wherein thecontacting step and/or the applying step is/are conducted at anysuitable pressure or at any pressure disclosed herein, e.g., from 5 psig(34 KPa) to 10,000 psig (68,948 KPa), from 45 psig (310 KPa) to 1000psig (6,895 KPa), etc.

Aspect 45. The process according to any one of Aspects 1-42, wherein thecontacting step and/or the applying step is/are conducted at anysuitable temperature or at any temperature disclosed herein, e.g., from0° C. to 250° C., from 0° C. to 95° C., from 15° C. to 70° C., etc.

Aspect 46. The process according to any one of the Aspects 1-43, whereinthe contacting step and/or the applying step is conducted at anysuitable weight hourly space velocity (WHSV) or any WHSV disclosedherein, e.g., from 0.05 to 50 hr⁻¹, from 1 to 25 hr⁻¹, from 1 to 5 hr⁻¹,etc., based on the amount of the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin.

Aspect 47. The process according to any one of Aspects 1-44, wherein theprocess further comprises a step of isolating the α,β-unsaturatedcarboxylic acid, or the salt thereof, e.g., using any suitableseparation/purification procedure or any separation/purificationprocedure disclosed herein, e.g., evaporation, distillation,chromatography, etc.

Aspect 48. The process according to any one of Aspects 1-45, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin of the contacting step a)is arranged as a fixed bed, a bubbling bed, a moving bed, or a stirredbed.

Aspect 49. The process according to any one of Aspects 1-45, wherein thesulfur oxoacid anion-substituted polyaromatic resin or the phosphorusoxoacid anion-substituted polyaromatic resin of the contacting step a)is formed into a bead, is supported onto an inert inorganic support, issupported onto an inert organic support, or is used in the absence of asupport.

Aspect 50. The process according to any one of Aspects 1-45, wherein thecontacting step a) is carried out by mixing/stirring the sulfonatedpolyaromatic resin or the phosphonated polyaromatic resin in thediluent.

Aspect 51. The process according to any one of Aspects 1-48, wherein theα,β-unsaturated carboxylic acid or the salt thereof comprises anysuitable α,β-unsaturated carboxylic acid, or any α,β-unsaturatedcarboxylic acid disclosed herein, or the salt thereof, e.g., acrylicacid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodiumacrylate, potassium acrylate, magnesium acrylate, sodium (meth)acrylate,etc.

Aspect 52. The process according to any one of Aspects 3-49, furthercomprising a step of contacting a transition metal precursor compoundcomprising at least one first ligand, an olefin, and carbon dioxide(CO₂) to form the metalalactone compound.

Aspect 53. The process according to any one of Aspects 3-49, furthercomprising a step of contacting a transition metal precursor compoundcomprising at least one first ligand, at least one second ligand, anolefin, and carbon dioxide (CO₂) to form the metalalactone compound.

Aspect 54. The process according to Aspect 51, wherein the metalalactonecompound comprises the at least one first ligand, the at least onesecond ligand, or a combination thereof.

Aspect 55. The process according to any one of Aspects 1-2 or 4-52,wherein the metalalactone compound comprises the at least one secondligand.

Aspect 56. The process according to any one of Aspects 3-53, wherein theolefin comprises any suitable olefin or any olefin disclosed herein,e.g. ethylene, propylene, butene (e.g., 1-butene), pentene, hexene(e.g., 1-hexene), heptane, octene (e.g., 1-octene), styrene, etc.

Aspect 57. The process according to any one of Aspects 3-54, wherein theolefin is ethylene, and the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) is conductedusing any suitable pressure of ethylene, or any pressure of ethylenedisclosed herein, e.g., from 10 psig (69 KPa) to 1,000 psig (6895 KPa),from 25 psig (172 KPa) to 500 psig (3,447 KPa), or from 50 psig (345KPa) to 300 psig (2,068 KPa), etc.

Aspect 58. The process according to any one of Aspects 3-55, wherein theolefin is ethylene, and the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) is conductedusing a constant addition of the olefin and carbon dioxide to providethe reaction mixture.

Aspect 59. The process according to Aspect 56, wherein the ethylene andcarbon dioxide (CO₂) are constantly added in an ethylene:CO₂ molar ratioof from 3:1 to 1:3, to provide the reaction mixture.

Aspect 60. The process according to any one of Aspects 3-57, wherein thestep of contacting a transition metal precursor compound with the olefinand carbon dioxide (CO₂) is conducted using any suitable pressure ofCO₂, or any pressure of CO₂ disclosed herein, e.g., from 20 psig (138KPa) to 2,000 psig (13,790 KPa), from 50 psig (345 KPa) to 750 psig(5,171 KPa), or from 100 psig (689 KPa) to 300 psig (2,068 KPa), etc.

Aspect 61. The process according to any one of Aspects 1-58, furthercomprising a step of monitoring the concentration of at least onereaction mixture component, at least one elimination reaction product,or a combination thereof.

Aspect 62. The process according to any one of Aspects 1-59, wherein themetal of the metalalactone or the metal of the transition metalprecursor compound is a Group 8-11 transition metal.

Aspect 63. The process according to any one of Aspects 1-59, wherein themetal of the metalalactone or the metal of the transition metalprecursor compound is Cr, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, W, Ag, Ir, Pt,or Au.

Aspect 64. The process according to any one of Aspects 1-59, wherein themetal of the metalalactone or the metal of the transition metalprecursor compound is Ni, Fe, or Rh.

Aspect 65. The process according to any one of Aspects 1-59, wherein themetal of the metalalactone or the metal of the transition metalprecursor compound is Ni.

Aspect 66. The process according to any one of Aspects 1-59, wherein themetalalactone is a nickelalactone, e.g., any suitable nickelalactone orany nickelalactone disclosed herein, or wherein the metal of thetransition metal precursor compound is Ni.

Aspect 67. The process according to any one of Aspects 1-64, wherein anyligand of the metalalactone compound, the first ligand, or the secondligand is any suitable neutral electron donor group and/or Lewis base,or any neutral electron donor group and/or Lewis base disclosed herein.

Aspect 68. The process according to any one of Aspects 1-64, wherein anyligand of the metalalactone compound, the first ligand, or the secondligand is a bidentate ligand.

Aspect 69. The process according to any one of Aspects 1-64, wherein anyligand of the metalalactone compound, the first ligand, or the secondligand comprises at least one of a nitrogen, phosphorus, sulfur, oroxygen heteroatom.

Aspect 70. The process according to any one of Aspects 1-64, wherein anyligand of the metalalactone compound, the first ligand, or the secondligand comprises or is selected from a diphosphine ligand, a diamineligand, a diene ligand, a diether ligand, or dithioether ligand.

Aspect 71. The process according to any one of Aspects 1-64, wherein anyligand of the metalalactone compound, the first ligand, or the secondligand comprises or is selected from a) an asymmetric ligand (comprisingdifferent donor atoms) such as 2-pyridylphosphine or b) anN-heterocyclic carbene (NHC) ligand.

Aspect 72. The process according to any one of Aspects 1-69, furthercomprising a step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin, by contacting a by-product acid form of the sulfuroxoacid anion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin that is generated from the processwith a metal-containing base or with a metal-containing salt.

Aspect 73. The process according to Aspect 72, wherein:

the metal-containing base comprises any suitable base, or any basedisclosed herein, e.g., carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, NaOH), alkoxides (e.g., Al(O^(i)Pr)₃,Na(O^(t)Bu), Mg(OEt)₂), aryloxides (e.g. Na(OC₆H₅), sodium phenoxide),sulfates (e.g. Na₂SO₄, K₂SO₄, CaSO₄, MgSO₄), etc.; and

the metal-containing salt comprises sodium chloride, potassium chloride,etc.

Aspect 74. The process according to any one of Aspects 1-69, furthercomprising a step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin by contacting a by-product resin that is generatedfrom the process with an aqueous sodium ion (Nat) source.

Aspect 75. The process according to any one of Aspects 1-69, furthercomprising a step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin by contacting a by-product resin that is generatedfrom the process with aqueous sodium halide (brine).

Aspect 76. The process according to any one of Aspects 1-69, furthercomprising a step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin by contacting a by-product resin that is generatedfrom the process with an aqueous acid and an aqueous brine.

Aspect 77. The process according to Aspect 74, wherein the by-productresin is contacted with aqueous acid followed by aqueous brine, orwherein the by-product resin is contacted with aqueous acid and aqueousbrine at the same time.

Aspect 78. The process according to Aspect 74, wherein the by-productresin is contacted with aqueous acid, followed by an aqueous wash step,followed by contacting with aqueous brine.

Aspect 79. The process according to any one of Aspects 1-69, furthercomprising a step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin by contacting a by-product resin that is generatedfrom the process with aqueous solution of about 5 wt % to about 15 wt %sodium chloride.

Aspect 80. The process according to any one of Aspects 70-77, furthercomprising a step of washing the regenerated sulfur oxoacidanion-substituted polyaromatic resin or the regenerated phosphorusoxoacid anion-substituted polyaromatic resin with a solvent or thediluent following the step of regenerating the sulfur oxoacidanion-substituted polyaromatic resin or the phosphorus oxoacidanion-substituted polyaromatic resin.

Aspect 81. The process according to any one of Aspects 70-77, whereinthe step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin is carried out in the absence of an alkoxide, anaryloxide, an amide, an alkylamide, an arylamide, an amine, a hydride, aphosphazene, and/or substituted analogs thereof.

Aspect 82. The process according to any one of Aspects 70-77, whereinthe step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin is carried out in the absence of an alkoxide, anaryloxide, a hydride, and/or a phosphazene.

Aspect 83. The process according to any one of Aspects 70-77, whereinthe step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin is carried out in the absence of an aryloxide or ametal hydride.

Aspect 84. The process according to any one of Aspects 70-77, whereinthe step of regenerating the sulfur oxoacid anion-substitutedpolyaromatic resin or the phosphorus oxoacid anion-substitutedpolyaromatic resin is carried out in the absence of a non-nucleophilicbase.

Aspect 85. The process according to any one of Aspects 70-77, whereinthe sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin is unsupported.

Aspect 86. The process according to any one of Aspects 70-77, whereinthe sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin is supported.

Aspect 87. The process according to any one of Aspects 1-84, wherein themetalalactone, the metalalactone ligand (that is, any ligand of themetalalactone compound other than the metalalactone moiety), thetransition metal precursor compound, the first ligand, the secondligand, the sulfur oxoacid anion-substituted polyaromatic resin or thephosphorus oxoacid anion-substituted polyaromatic resin, or the metalcation is any suitable metalalactone, additional ligand of themetalalactone compound, transition metal precursor compound, firstligand, second ligand, sulfonated polyaromatic resin or the phosphonatedpolyaromatic resin, or metal cation or is any metalalactone,metalalactone ligand, sition metal precursor compound, first ligand,second ligand, sulfur oxoacid anion-substituted polyaromatic resin orphosphorus oxoacid anion-substituted polyaromatic resin, or metal cationdisclosed herein.

Aspect 88. A process for forming an α,β-unsaturated carboxylic acid orsalt thereof, the process comprising:

-   -   (1) contacting        -   (a) a metalalactone comprising a Group 8-10 metal and at            least one ligand;        -   (b) a diluent; and        -   (c) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   (2) applying reaction conditions to the reaction mixture        suitable to induce a metalalactone elimination reaction to form        the α,β-unsaturated carboxylic acid or the salt thereof.

Aspect 89. A process for forming an α,β-unsaturated carboxylic acid or asalt thereof, the process comprising:

-   -   (1) contacting in any order        -   (a) a group 8-11 transition metal precursor;        -   (b) an olefin;        -   (c) carbon dioxide (CO₂);        -   (d) a diluent; and        -   (e) a sulfur oxoacid anion-substituted polyaromatic resin or            a phosphorus oxoacid anion-substituted polyaromatic resin;            wherein the polyaromatic resin further comprises associated            metal cations to provide a reaction mixture; and    -   (2) applying reaction conditions to the reaction mixture        suitable to produce the α,β-unsaturated carboxylic acid or the        salt thereof.

Aspect 90. A process for forming an α,β-unsaturated carboxylic acid or asalt thereof, the process comprising:

-   -   (1) contacting in any order    -   (a) a group 8-11 transition metal catalyst;    -   (b) an olefin;    -   (c) carbon dioxide (CO₂);    -   (d) a diluent; and    -   (e) a sulfur oxoacid anion-substituted polyaromatic resin or a        phosphorus oxoacid anion-substituted polyaromatic resin; wherein        the polyaromatic resin further comprises associated metal        cations to provide a reaction mixture; and    -   (2) contacting the reaction mixture with a metal-containing base        selected from an alkali metal or an alkaline earth metal oxide,        hydroxide, alkoxide, aryloxide, amide, alkyl amide, arylamide,        or carbonate to produce an α,β-unsaturated carboxylic acid salt;    -   wherein the contacting step is carried out in the absence of a        non-nucleophilic base.

The invention claimed is:
 1. A catalyst system for forming anα,β-unsaturated carboxylic acid or a salt thereof, the catalyst systemcomprising: a) a transition metal precursor comprising a Group 8-11transition metal and at least one first ligand; b) optionally, at leastone second ligand; c) an olefin; d) carbon dioxide (CO₂); e) a diluent;and f) an oxoacid anion-substituted polyaromatic resin comprising asulfonated polyaromatic resin, a phosphonated polyaromatic resin, asulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinatedpolyaromatic resin, and further comprising associated metal cations. 2.The catalyst system according to claim 1, wherein the catalyst systemfurther comprises a Group 8-11 transition metal metalalactone compoundor an adduct of a Group 8-11 transition metal metalalactone compound andthe oxoacid anion-substituted polyaromatic resin.
 3. The catalyst systemaccording to claim 1, wherein the oxoacid anion-substituted polyaromaticresin has a) an average particle size from about 0.1 mm to about 1.0 mm,b) an average pore diameter from about 50 nm to about 250 nm, or c) bothan average particle size from about 0.1 mm to about 1.0 mm and anaverage pore diameter from about 50 nm to about 250 nm.
 4. The catalystsystem according to claim 1, wherein: the oxoacid anion-substitutedpolyaromatic resin is formed into a bead, supported onto an inertinorganic support, supported onto an inert organic support, or used inthe absence of a support; and the oxoacid anion-substituted polyaromaticresin is arranged as a fixed bed, a bubbling bed, a moving bed, or astirred bed.
 5. The catalyst system according to claim 1, wherein: themetal of the transition metal precursor compound is Ni, and wherein thefirst ligand and the second ligand are selected independently from adiphosphine ligand, a diamine ligand, a diene ligand, a diether ligand,or dithioether ligand; and the associated metal cations are selectedfrom a Group 1, 2, 12, or 13 metal.
 6. The catalyst system according toclaim 1, wherein the diluent comprises an ether diluent, acarbonyl-containing diluent, an aromatic hydrocarbon diluent, ahalogenated aromatic hydrocarbon diluent, or an alcohol diluent.
 7. Thecatalyst system according to claim 1, wherein the olefin comprisesethylene, propylene, butene, pentene, hexene, heptane, octene, orstyrene.
 8. The catalyst system according to claim 1, wherein theα,β-unsaturated carboxylic acid or the salt thereof is acrylic acid,methacrylic acid, 2-ethylacrylic acid, cinnamic acid, or a salt thereof.9. A process for forming an α,β-unsaturated carboxylic acid or a saltthereof, the process comprising: a) contacting in any order 1) atransition metal precursor comprising a Group 8-11 transition metal andat least one first ligand; 2) optionally, at least one second ligand; 3)an olefin; 4) carbon dioxide (CO₂); 5) a diluent; and 6) an oxoacidanion-substituted polyaromatic resin comprising a sulfonatedpolyaromatic resin, a phosphonated polyaromatic resin, a sulfinatedpolyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromaticresin, further comprising associated metal cations, to provide areaction mixture; and b) applying reaction conditions to the reactionmixture suitable to form the α,βunsaturated carboxylic acid or the saltthereof.
 10. The process according to claim 9, wherein the reactionmixture comprises a Group 8-11 transition metal metalalactone compoundor an adduct of a Group 8-11 transition metal metalalactone compound andthe oxoacid anion-substituted polyaromatic resin, and wherein thereaction conditions suitable to form the α,βunsaturated carboxylic acidor the salt thereof induces a metalalactone elimination reaction toproduce the α,β-unsaturated carboxylic acid or the salt thereof.
 11. Theprocess according to claim 9, wherein the oxoacid anion-substitutedpolyaromatic resin has a) an average particle size from about 0.1 mm toabout 1.0 mm, b) an average pore diameter from about 50 nm to about 250nm, or c) both an average particle size from about 0.1 mm to about 1.0mm and an average pore diameter from about 50 nm to about 250 nm. 12.The process according to claim 9, wherein: the oxoacid anion-substitutedpolyaromatic resin is formed into a bead, supported onto an inertinorganic support, supported onto an inert organic support, or used inthe absence of a support; and the oxoacid anion-substituted polyaromaticresin is arranged as a fixed bed, a bubbling bed, a moving bed, or astirred bed.
 13. The process according to claim 9, wherein: the metal ofthe transition metal precursor compound is Ni, and wherein the firstligand and the second ligand are selected independently from adiphosphine ligand, a diamine ligand, a diene ligand, a diether ligand,or dithioether ligand; and the associated metal cations are selectedfrom a Group 1, 2, 12, or 13 metal.
 14. The process according to claim9, wherein the diluent comprises an ether diluent, a carbonyl-containingdiluent, an aromatic hydrocarbon diluent, a halogenated aromatichydrocarbon diluent, or an alcohol diluent.
 15. The process according toclaim 9, wherein the contacting step and/or the applying step is/areconducted at a pressure from 5 psig (34 KPa) to 10,000 psig (68,948 KPa)and at a temperature from 0° C. to 250° C.
 16. The process according toclaim 9, wherein the olefin comprises ethylene, propylene, butene,pentene, hexene, heptane, octene, or styrene.
 17. The process accordingto claim 9, wherein the α,β-unsaturated carboxylic acid or the saltthereof is acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamicacid, or a salt thereof.
 18. The process according to claim 9, furthercomprising a step of regenerating the oxoacid anion-substitutedpolyaromatic resin and associated cations by contacting a by-productacid form of the oxoacid anion-substituted polyaromatic resin with ametal-containing base or a metal-containing salt.
 19. The processaccording to claim 9, wherein the olefin is ethylene, and the step ofcontacting a transition metal precursor compound with the olefin andcarbon dioxide (CO2) is conducted using a constant addition of theolefin and carbon dioxide in an ethylene:CO₂ molar ratio of from 3:1 to1:3, to provide the reaction mixture.
 20. A catalyst system for formingan α,β-unsaturated carboxylic acid or a salt thereof, the catalystsystem comprising: a) a transition metal precursor comprising a Group8-11 transition metal and at least one first ligand; b) optionally, atleast one second ligand; c) an olefin; d) carbon dioxide (CO₂); e) adiluent; and f) an oxoacid anion-substituted styrene-based polymer orcopolymer comprising a sulfonated, a phosphonated, a sulfinated, athiosulfonated, or a thiosulfinated styrene polymer orstyrene-divinylarene copolymer, further comprising associated metalcations.
 21. The catalyst system according to claim 1, wherein theoxoacid anion-substituted polyaromatic resin comprises a sulfonated-, aphosphonated-, a sulfinated-, a thiosulfonated-, or athiosulfinated-styrene polymer or styrene-divinylarene copolymer. 22.The catalyst system according to claim 1, wherein the oxoacidanion-substituted polyaromatic resin comprises a crosslinked polystyrenesulfonate resin.
 23. The catalyst system according to claim 1, whereinthe oxoacid anion-substituted polyaromatic resin comprises asulfonated-, a phosphonated-, a sulfinated-, a thiosulfonated-, or athio sulfinated-phenol-formaldehyde resin, polyhydroxyarene-formaldehyderesin, or polyhydroxyarene- and fluorophenol-formaldehyde resin.
 24. Thecatalyst system according to claim 1, wherein the oxoacidanion-substituted polyaromatic resin comprises a sulfonated-, aphosphonated-, a sulfinated-, a thiosulfonated-, or athiosulfinated-resorcinol-formaldehyde resin, or resorcinol- and 2-fluorophenol-formaldehyde resin.
 25. The catalyst system according toclaim 1, wherein the oxoacid anion-substituted polyaromatic resin ismacroreticular.
 26. The catalyst system according to claim 1, whereinthe metal of the transition metal precursor compound is a Group 8 metal.27. The catalyst system according to claim 1, wherein the metal of thetransition metal precursor compound is a Group 9 metal.
 28. The catalystsystem according to claim 1, wherein the metal of the transition metalprecursor compound is a Group 10 metal.
 29. The catalyst systemaccording to claim 1, wherein the metal of the transition metalprecursor compound is a Group 11 metal.
 30. The catalyst systemaccording to claim 1, wherein the metal of the transition metalprecursor compound is Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, or Au.
 31. Thecatalyst system according to claim 1, wherein the first ligand is1,5-cyclooctadiene and the second ligand is a diphosphine ligand, adiamine ligand, or an asymmetric ligand having one nitrogen and onephosphorus donor atom.
 32. The catalyst system according to claim 1,wherein the associated metal cations are an alkali metal, an alkalineearth metal, or a combination thereof.